TW200933951A - Process for making contained layers and devices made with same - Google Patents

Abstract

There is provided a process for forming a contained second layer over a first layer. The process comprises forming the first layer having a first surface energy and then treating the first layer with a photocurable surface-active composition which is a fluorinated ester or fluorinated imide of an α, β - unsaturated polyacid; exposing the photocurable surface-active composition patternwise with radiation resulting in exposed areas and unexposed areas; developing the photocurable surface-active composition to remove the unexposed areas resulting in a first layer having untreated portions in the unexposed areas and treated portions in the exposed areas, where the treated portions have a second surface energy that is lower than the first surface energy; and forming the second layer on the untreated portions of the first layer. There is also provided an organic electronic device made by the process.

Description

200933951 IX. INSTRUCTIONS: TECHNICAL FIELD OF THE INVENTION The present disclosure relates generally to a method of fabricating an electronic device. It is also related to a device made by this method. This application is based on 35 USC § 119(e). The application for the application of the US Provisional Application No. 60/982,927 and May 16, 2008; The priority of /053,687, the entire contents of both of which are incorporated herein by reference. φ [Prior Art] Electronic devices using organic active materials exist in many different types of electronic devices. In such devices, the organic active layer is sandwiched between two electrodes. One type of electronic device is an organic light emitting diode (OLed) ^ 〇 LED is expected to be used for display applications due to its high power conversion efficiency and low processing cost. These displays are particularly promising for battery powered portable electronic devices (including cellular phones, personal digital assistants, palmtop personal computers, and DVD players). These applications require displays with high information content, full color and fast video response time, in addition to low power consumption. The current research to produce full-color 〇LEDs is aimed at the development of cost-effective, high-volume methods for producing color pixels. For the production of monochrome displays by liquid processing, spin coating has been widely used (see, for example, David Braun and

Alan J. Heeger, Appl. Phys Letters 58,1982 (1991)). However, the manufacture of full color displays requires some improvement in the procedures used to make monochrome displays. For example, to make a display with full-color images, 135696.doc 200933951 divides each display pixel into three sub-pixels, each of which emits one of three original dominant colors (red, green, and blue). This division of panchromatic pixels into one sub-pixel requires improvement of the current method to prevent liquid colored material (i.e., ink) from spreading and color mixing. Several methods for providing ink wraps are described in the literature. These methods are based on the surrounding structure, surface tension discontinuity, and a combination of the two: #为为的几何的几何障碍: Pixel well, bank structure, etc. In order to have an effective _ & 'the structure must be large, comparable to the wet thickness of the material being deposited. When ® 胄 emissive ink is printed in these structures, it Μ the surface of the structure, so the thickness uniformity near the structure is reduced. Because, oh, the structure must be moved to the emitter "pixel" area outside so that the inhomogeneity is not significant in operation. Since the space on the display (especially for high resolution displays) is limited, it reduces the available emission area of the pixels. The actual surrounding structure is generally deposited in the charge injection layer and

The continuous layer of the charge transport layer has a negative impact on quality. Therefore, all layers must be printed. V 〇 In addition, surface tension $ continuity is obtained in the presence of a printed or vapor deposited region of low surface tension material. These low surface tension materials—the organic-active layer—are applied before printing or coating on the pixel area... :m When using a continuous non-emissive layer, use this (four) sound quality, so all layers must be printed . An example of a combination of two ink containment techniques is a cf4-electropolymerization process of a photoresist bank (pixel well, channel). In general, all active layers must be printed in the pixel region. All of these wraps have the drawback of hindering continuous coating. Continuous coating 135696.doc 200933951 is required - as a result of higher yields and lower equipment costs. Therefore, there is a need for an improved method of forming an electronic device. SUMMARY OF THE INVENTION The present invention provides a method of forming a second layer on a first layer, the method comprising: - forming a first layer having a first surface energy; a photocurable surface of the constituent materials of the group • The active composition treats the first 35: ", β_不鲜多(四) fluorinated vinegar, & alpha, beta-unsaturated polybasic acid fluorinated quinone imine and a combination; exposing the photocurable surface active composition to a radiation-producing exposed area and an unexposed area; developing the photocurable surface active composition to remove the photocurable surface active composition from the unexposed area, a first layer having an untreated portion having an untreated portion and having a treated portion in the exposed portion, wherein the treated portion has a second surface energy lower than the first surface energy; and the untreated portion of the first layer A second layer is formed on the portion. The present invention provides a method of fabricating an organic electronic device comprising a first organic active layer and a second organic active layer on an electrode, the method comprising: forming a first organic layer having a first surface energy on an electrode; The photocurable surface active composition of the material of the following composition groups treats the first organic layer: a fluoride of α,β-unsaturated polybasic acid, a fluorinated imine of an α,β-unsaturated polybasic acid, and a combination; the photocurable surface active composition is exposed to radiation in a pattern to produce an exposed area and an unexposed area; 135696.doc 200933951 Photocurable surface active composition is applied to render the photocurable surface active composition from Exposure zone removal resulting from a first organic active layer having an untreated portion in the unexposed portion and having a treated portion in the exposed region, wherein the treated portion has a second surface energy lower than the first surface energy; and A second organic layer is formed on the untreated portion of the first organic active layer. The present invention also provides an organic electronic device comprising a first organic active layer and a second organic active layer on the electrode, and additionally comprising a patterned photocurable surface active group composition, wherein the second organic The active layer is only present in the region where the photocurable surface active composition is absent, wherein the photocurable surface active composition is made of a material selected from the group consisting of: α,β-unsaturated polybasic acid A fluorinated ester, an alpha, a vaporized quinone imine of a polyunsaturated polybasic acid, and combinations thereof. The above general description and the following detailed description are intended to be illustrative and not restrictive. [Embodiment] The embodiments are described with reference to the drawings to improve the understanding of the concepts presented herein. Those skilled in the art will understand that the objects in the figures are illustrated for simplicity and clarity and are not necessarily to scale. For example, the dimensions of some of the items in the figures may be exaggerated relative to the other items to help improve understanding. The present invention provides a method of forming a wrap-around second layer on a first layer, the method comprising: 135696 .doc 200933951 Forming a first layer having a first surface energy; treating the first layer with a photocurable surface active composition comprising a material selected from the group consisting of: fluorination of an alpha, beta-unsaturated polybasic acid Fluorinated quinone imine of ester, α,β-unsaturated polybasic acid and combinations thereof; • Exposing the photocurable surface active composition to radiation in a pattern to produce exposed and unexposed areas; The surface active composition is developed to remove the photocurable surface active composition from the unexposed area, resulting in a first layer having an untreated portion of the unexposed portion and having a treated portion in the exposed portion, wherein the treated A portion has a second surface energy lower than the first surface energy; and a second layer is formed on the untreated portion of the first layer. Many aspects and embodiments have been described above, and are merely illustrative and non-limiting. After reading this specification, those skilled in the art will appreciate that other aspects and embodiments are possible without departing from the scope of the invention. Other features and advantages of any one or more of the embodiments will be apparent from the following description. The embodiments first discuss the definition and description of the terms, followed by the photocurable surface active composition, the method, the organic electronic device, and finally the examples. 1. Definitions and Description of Terms Before describing the details of the embodiments described below, some terms are defined or explained. When m is produced in the layer or material, it means a layer or material that exhibits electrical or electrical radiation characteristics. In electronic devices, the active material electronically facilitates the operation of the device. Examples of active materials include (but are limited to) conduction, implantation, 135696.doc 200933951 materials that transport or block charge, where ψ, 3 ^ T1: what can be electrons or holes; and hair = or when receiving radiation Examples of materials that exhibit electron-holes for Hanta's variation include, but are not limited to, planarizing materials, insulating materials, and environmental barrier materials. The super-emission of the sacred sacred sacred sacred sacred sacred sacred sacred sacred sacred sacred sacred sacred sacred sacred sacred sacred It has a natural tendency to spread out the deposited areas. The »思»亥层 can be surface energy effect or ❹

The combination of the surface energy effect and the physical barrier structure surrounds the package. The term "electrode" means a component or structure within an electronic component that is configured to transport carriers. For example, the electrodes can be anodes, cathodes, capacitor electrodes, gate electrodes, and the like. The electrodes can include portions of transistors, capacitors, resistors, inductors, diodes, electronic components, power supplies, or any combination thereof. The term "fluorinated" when referring to an organic compound means that one or more hydrogen atoms in the compound have been replaced by fluorine. This term covers both partially and fully fluorinated materials. The term "layer" is used interchangeably with the term "film" and refers to a coating that covers the desired area. The term is not limited by size. The area can be as large as the entire device or as small as the actual visual display. The functional area, or as small as a single sub-pixel. The layers and films can be formed by any conventional deposition technique including: vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer. Highly patterned or may be integral and unpatterned. The term "liquid composition" means a liquid medium that dissolves a material to form a solution, disperses the material to form a liquid medium or suspension material of the dispersion to form a suspension or Liquid medium for emulsions. 135696.doc 200933951 The term "liquid enclosure structure" means a structure in or on a workpiece, wherein the one or more structures themselves or together act to limit the liquid when the liquid flows over the workpiece or The main function that guides a certain area or range. The liquid enclosure structure can include a cathode separator or well structure. • The term "liquid media" means liquid materials, including pure liquids, liquids, liquids, solutions, dispersions, suspensions, and emulsions. Use a liquid medium regardless of whether: one or more solvents are present. The term "organic electronic device" means a device comprising one or more organic semiconductor layers or Φ materials. Organic electronic devices include, but are not limited to: (1) devices that convert electrical energy into radiation (eg, light-emitting diodes, light-emitting diode displays, one-pole lasers or illumination panels); (2) use electronic methods to detect a device for measuring signals (eg, optical debt detectors, photoconductive cells, photoresists, optical switches, optoelectronic crystals, photocells, infrared (&"IR") detectors or biosensors); (7) devices that convert radiation into electrical energy (eg, optoelectronic device or solar cell); (4) a device (eg, a transistor or a diode) comprising one or more electronic φ components including one or more organic semiconductor layers, or (1) to (4) Any combination of devices in the item. The term photocurable " means a radiation-sensitive composition or layer that becomes more adhered to the surface when exposed to radiation: on the surface or more difficult to remove from the surface. The term "photocurable surface active composition" means a composition comprising at least one photocurable material, and when the composition is applied to a layer, the surface of the layer can be lowered. The term is abbreviated as "PCSA" and refers to a composition that is exposed before and after exposure. The term "photocurable surface active composition" refers to a photocurable surface active composition that has been formed into a layer and exposed to radiation after 135696.doc -12.200933951. The term "polyacid" means an organic compound having two or more acidic groups. The term "light shot" means the addition of any form of energy, including any form of , , , or electromagnetic wave 4 or subatomic particles, whether in the form of rays, waves or particles. The term "light shot sensitivity" when referring to a material means exposure to at least one chemical, physical or electrical property of the material.

The term "surface energy" is the amount of energy required to produce a surface per unit area from a material. A surface material characterized by a liquid material having a relatively surface energy will not wet the surface having a sufficiently low surface energy. The term 'unsaturated" when referring to an organic compound means that the compound has at least one carbon-carbon double bond or carbon-carbon bond. The term "α,Ρ_unsaturated" means that a double bond or a conjugate is conjugated to an acid functional group. The term "in" as used herein does not necessarily mean that a layer, member or structure is directly abutting or contacting another layer 'component or structure. There may be additional intervening layers, components or structures. The term "comprising", "including", "including", ",", "includes", or any other variation thereof, is intended to cover a non-exclusive inclusion. For example, a process, method, article or device comprising a series of components It is not necessarily limited to the components, but may include other components not specifically listed or inherent to the process, method, article, or device. In addition, 'unless expressly stated otherwise, 'or,' means implied or Rather than exclusion or. For example, the condition Α or Β satisfies any of the following: A is true (or exists) and B is false (or does not exist), a is 135696.doc -13- 200933951 False (or not Exists) and B is true (or exists), and both are true (or exist and 'used'-" are used to describe the components and components described herein. This is for convenience only and gives the present invention The general meaning of the mouth is used. Unless explicitly stated otherwise, this description should be understood to include one or at least one and the singular also includes the plural. 'The number of the family in the periodic table is as (4) (8) : , the first Seen "New • Notes" conventions. © Unless (4) Definitions ′ All technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art, although The methods and materials in which the methods and materials are similar or equivalent are to practice or test the embodiments of the present invention, but suitable methods and materials are as follows. Unless otherwise recited, all publications and patents mentioned herein. Applications, patents, and other references are incorporated by reference in their entirety. In the event of a conflict, the text, methods, and examples are illustrative and not intended. To the extent not described herein, the specific materials, processing behaviors, and: many of the details of the road are well known and can be found in organic light-emitting diodes to display the stomach, detectors, optoelectronics and In textbooks and other sources within semiconductor component technology. 2. Photocurable surface active composition photocurable surface active composition ("PCSA") is a radiation-sensitive composition. When exposed to light radiation, the PCSA reacts to form a better adhesion to the surface than the material not exposed to 135696.doc -14 - 200933951 or more difficult to Surface removed material. Treatment with PCSA reduces the surface energy of the treated material.

Radiation can be any type of light that causes the PCSA to produce the desired physical change. In an embodiment the light-lighting system is selected from the group consisting of infrared radiation, visible light radiation, ultraviolet radiation, and combinations thereof. In an embodiment, the light project is selected from the group consisting of visible light radiation and ultraviolet radiation. In one embodiment, the light shot has a wavelength in the range of (10) to the full nm. In an embodiment, the radiation is far UV (four) having a wavelength in the range of paralysis (10). In another embodiment t, the ultraviolet light has a slightly longer wavelength in the range of 300-400 nm. In another embodiment, the light shot has a wavelength in the range of 400 to 450 nm. In certain embodiments, the PCSA can be applied by solvent or by vapor deposition. In certain embodiments, the pcSA has a vapor pressure that is sufficiently low to prevent undesired evaporation after it is applied to form the treated first layer. In certain embodiments, the PCSA does not react in the absence of radiation to form a non-developable material. PCSA comprises a fluorinated ester of an alpha, beta-unsaturated polybasic acid or a quinone imine. The acidic group can be selected from the group consisting of tracism, acid, sulphur and combinations thereof. In certain embodiments, the polyacid is a polyacid. In certain embodiments, the polyacid is linear. In certain embodiments, the polybasic acid is branched. In certain embodiments, the polybasic acid may contain more than one unit of unsaturation. In certain embodiments, the polybasic acid is substituted. In certain embodiments, this substitution incorporates one or more oxygen atoms into the hydrocarbon backbone of the unsaturated polyacid. In certain embodiments, this substitution is attached to the hydrocarbon backbone of the unsaturated polyacid. In certain embodiments, this substitution contains a fluorine atom. 135696.doc • 15-200933951 ^In some embodiments, all acidic groups are shared with unsaturated groups. In a certain embodiment, only one acidic group is conjugated to an unsaturated group. f In certain embodiments, PCSA is at least 5 G% fluorinated, which means bonded to carbon, which can be replaced by fluorine in 50% of the hydrogen atoms. In certain embodiments, the PCSA is fluorinated to 6 〇 〇; in some embodiments at least 70. /. Fluorinated. In certain embodiments, 'PCSA is a non-aromatic alpha, beta-unsaturated polybasic acid vinegar or quinone imine. Examples of non-aromatic α'β-unsaturated polybasic acids include, but are not limited to, fumaric acid, maleic acid, itaconic acid, 2,2-diindolyl-4-methylenepentylene Acid, muconic acid 2-ylidene glutaric acid, yttrium acid, acid, bismuth dibasic acid and hexamethylene-2-alkylic acid and methacrylic acid oligomer. pCSA can comprise a Or a combination of a plurality of unsaturated polybasic acid fluorinates or quinones, or fluorinated vinegars or quinones of unsaturated polybasic acids and fluorinated unsaturated monobasic acids. In certain embodiments, the esters are fluorinated alcohols. (Rf〇H) is formed. The Rf group has 4-15 carbon atoms, and 〇-5 are pendant oxygen atoms and at least 4 fluorine atoms contained in the carbon atom chain, and the restriction condition is that it has 〇H There is no fluorine atom on the carbon atom. The fluorinated alcohol may be linear or branched, saturated or unsaturated. In certain embodiments, the alcohol has one of the following formulas: HO-(CR, R2)- (CH2)s-{(CRaF2.aOb)r(CR=CROb)w}-CHcF3.c or HO-(CR,R2)-CH[(CH2)s-{(CRaF2.a〇b)r(CR =CROb)w}-CHcF3.c]2 where a, b, c, p, s, 1 and w are the same or different at each occurrence and are integers, and a=0-2 b=0-l, 135696.doc 16- 200933951 c=0-3 , R=H or (CHaF2.a)pF, R1, R2=H or CpH2p+i, p=l-3, s=0-5 , t=2-l5 and w=l-2 groups in parentheses {} can be arranged in any order

Farewell. In some embodiments, 4 <t =0 or =H or , 99. In certain embodiments, 3 = 2 or 3. In some embodiments +w£l2. In some embodiments, c = 〇. In certain embodiments, v 1 ° is in some embodiments a = 〇. In certain embodiments, R CF3. In certain embodiments, r1 = r2 = h. In some embodiments RLRLCHs. Some non-limiting examples of fluorinated alcohols include

F2 f2 f2 Hcr"^c, c/c, czc'CF f2 f2

F2 f2 f2 ho VIII VC^C, C, C, CF3 f2 f2 f2 H〇^^C, c/Ccf-CF3 F2 CF3 135696.doc 200933951 f2

HO c〆 F2 c , cr f2 f2 c.c.cf3 f2 cf3 V c2 HO into c〆, 〇/C, C〆 F2 F2 F2 f2 f2 HO eight czC, C, C, (TC, CF3 f2 f2 f2 f2 f2

H〇/\^C, C-C, C, CF3 f2 f2

3 F2 f2 f2 f2 C, /C, cw f2 f2 3 f2 f2 f2 f2 H〇A, /c, crc, crc, (rc, cF3 F2 f2 f2 3 F2 F2 F2 F2 f2

Hcr^/c, crc, crc, crc, crc, cFq F2 f2 f2 f2 3 F2 f2 f2 ho broad 'c, c, c/c, crc, crCF3 F2 F2 f2 f2 In certain embodiments, the amine system It is formed using a fluorided amine (RfNH2). The Rf group has 4-15 carbon atoms '〇_5 oxygen atoms contained in the carbon atom chain and at least 4 (four) atoms'. The restriction condition is that the atom has a ·2 atom: no J35696.doc • /8- 200933951 at l atom. The gasified amine can be a straight or branched chain, saturated or unsaturated. In certain embodiments, the amine has one of the formula: H2N-(CR1R2)-(CH2)s-{(CRaF2.a 〇b)r(CR=CR〇b)w}.CHcF3.c or H2N-(CR,)[-(CH2)s-{(CRaF2.a〇b)t.(CR=CR〇b)w} CHcF3 ch • where a, b, c, s, t&w are the same or different at each occurrence, and are integers, and a=0-2, © b=0-l, c=0_3, R=H Or (CHaF2_a)pF, R1, R2=H or CpH2p+1, p=1 -3, s=0-5, t=2-15, and -w=l-2.团 The groups in parentheses {} can be arranged in any order. In some embodiments, 19 < In some embodiments, 8=2 or ^ in some embodiments, 乜: 矸2. In some embodiments, c=〇. In some embodiments, w = 〇 or 1. In some embodiments, In certain embodiments, R = h or CF3 » In certain embodiments, r1 = r2 = h. In certain embodiments, R丨=R2=CH3. Some non-limiting examples of amines include: 135696.doc 200933951 f2 F2 f2 f2 F2 f2 f2 f2 ❹ F2 f2 F, F2 F〇h2n oc Cc2, 〆F2 f2 f2 f2 H2N^^C-c"C'C"C"CF3 f2 f2 F2 'CF, F2 f2

F2 f2 f2 H2N,^X^C^C'C^C"CF3 F2 F2 f2 H2Nx^^C-C^CCFCF3

Fz CF3. Additional examples of fluorinated alcohols and amines can be found, for example, in J. Fluorine Chemistry 77 (1996) 193-194; J. Fluorine Chemistry 80 (1996) 13 5-144; and U.S. Patents 6,479,612 and 7,138,551. • 20-135696.doc 200933951 When PCSA is brewed, all acidic groups of the α,β-unsaturated polybasic acid are serialized and at least one acidic group is esterified with a fluoroalkyl group. In certain embodiments, all of the acidic groups of the alpha, beta-unsaturated polybasic acid are esterified with a fluoroalkyl group. When PCSA is an enamine, all of the acidic groups of the α,β-unsaturated polybasic acid are imidized by hydrazine and at least two acidic groups are imidized with the fluoroalkyl hydrazine. In certain embodiments, all of the acidic groups in the alpha, beta-unsaturated polybasic acid are aminated with a fluoroalkyl group. The PCSA may additionally comprise a fluorinated ester of an α,β-unsaturated polybasic acid or a combination of a quinone imine with a fluorinated ester of an α,β·unsaturated monobasic acid or a fluorinated brewed imine or decylamine. These esters, guanamines and quinones can be made from the above alcohols and amines. Examples of α,ρ_unsaturated monobasic acids include, but are not limited to, acrylic acid, methacrylic acid, α•hydroxy methacrylic acid, and α-gas methacrylic acid. The PCSA composition may additionally comprise an adjuvant, including a stabilizer, a flow enhancing J plasticizer, a photoinitiator, a photoradical generator, and other components designed to enhance the methods described herein. In certain embodiments 'PCSA is selected from the group consisting of: bis(3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorooctyl) Base) fumaric acid vinegar; double (' '4,4,5'5,6'6,7,7,8,8,8-tridecafluorooctyl) maleate; 3'3,4,4,6'6,7,7'8,8,8-decafluoro-5-oxa-octyl)cis- decenedicarboxylate; double (3,3,5,5 ,6,6,7,7,8,8,8-decafluorooctyl) cis-butane diacetate; enediminoimine; double (3,3,4,4,5,5,6, 6,7,7,8,8,8-tridecafluorooctyl) itaconic acid vinegar; 135696.doc -21- 200933951 顺,顺·双 (3,3,4,4,5,5,6, 6,7,7,8,8,8-tridecafluorooctyl) muconate;

Bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)_hex-bu (£)-ene-4-yne-1 6-diester; bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)acetylene dicarboxylate;

Bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-2-phenylcis succinate; double (3, 3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-2-benzylidene malonate; bis(CH2CH2OCH2CH2OCF2C(H)FOC3F7) Butenoic acid ester; bis(CH2CH2OCF2C(H)FOC3F7) maleate; bis(CH2CH2CH2OCF2C(H)FOC3F7) maleate; bis(3,3,4,4,5,5, 6,6,7,7,8,8,8-tridecafluorooctyl) 1 -toluene oxyalkyleneethyl-1,2-dicarboxylate; four (3,3,4,4,5 , 5,6,6,7,7,8,8,8-tridecafluorooctyl)ethylidene tetracarboxylate; and combinations thereof. In certain embodiments, the photoinitiator is present in a separate layer that is in contact with the layer containing the PCSA. The photoinitiator layer can increase the reaction rate of PCSA and/or reduce the desired dose. In certain embodiments, a photoinitiator layer is first formed and a PCS A layer is applied to and in contact with the photoinitiator layer. In certain embodiments, a photoinitiator is applied to and in contact with the PCSA layer. 135696.doc -22- 200933951 Photoinitiators are well known and any such materials may be used as long as they interact with PCSA to effect curing and as long as they do not adversely affect device performance. Examples of types of photoinitiators include, but are not limited to, heart hydroxyketone, phenylglyoxylate, ketal, alpha-amino ketone, decyl phosphine, phosphine oxide, ruthenium, and mineral salts. Combinations and mixtures of photoinitiators can also be used. Two commercially available photoinitiators suitable for use in the present invention are Irgacure 184 and Darocur 1173 (available from Ciba Corporation).

The Irgacure 184 Darocur 1173 photoinitiator layer can include other materials such as coating aids and binders. In certain embodiments, the photoinitiator layer consists essentially of a photoinitiator. The photoinitiator layer can be formed by any known technique including solution deposition, vapor deposition, and heat transfer. In general, 'PCS A materials can be made using techniques known in organic chemistry. The physical distinction between the PCSA region exposed to radiation and the pcsA region not exposed to radiation (hereinafter referred to as "development") can be achieved by any known technique. These technologies have been widely used in photoresist technology. Examples of development techniques include, but are not limited to, application of heat and/or vacuum (evaporation), treatment with a liquid medium (washing), treatment with an adsorbent material (absorption), treatment with a viscous material, and the like. 135696.doc -23- 200933951 In one embodiment, pCSA reacts with the underlying region upon exposure to radiation. The exact mechanism of this reaction will depend on the materials used. In another embodiment, the PCSA forms a non-volatile or insoluble material that adheres to the underlying region without chemical bonding to the underlying region. In addition, the exact mechanism of this reaction will depend on the materials used. After exposure to radiation, the PCSA in the unexposed areas is removed by suitable development processing. In some embodiments, only the PCSA in the unexposed zone is removed. In some embodiments, the pcSA in the exposed area is also partially removed, leaving a thin layer in the areas. In some embodiments, the PCSA remaining in the exposed zone is less than 50 A thick. In some embodiments, the thickness of the PCSA remaining in the exposed zone is substantially a single layer. 3. Method In the method provided herein, a first layer is formed, the first layer is treated with a photocurable surface active composition ("PCSA"), pcsA is exposed to radiation, and PCSA is developed to expose PCSA from unexposed. Zone removal results from a first layer having an untreated portion in the unexposed portion and a treated portion in the exposed region. The treated portion has a second surface energy that is lower than the first surface energy. A second layer is formed on the untreated portion of the first layer. In an embodiment, the first layer is a substrate. The substrate can be inorganic or organic. Examples of substrates include, but are not limited to, glass, ceramics, polymeric films (such as poly-branched and polyimide films), metals, and metal oxides. In an embodiment, the first layer is an electrode. The electrodes may be unpatterned or patterned. In one embodiment, the electrodes are patterned in parallel lines. Alternatively, the electrodes can be an array of patterned structures having planar shapes such as squares, rectangles, circles, triangles, ellipses, and the like. Electrode 135696.doc •24· 200933951 Available on the substrate. In one embodiment, the first layer is deposited on the substrate. The first layer can be patterned or unpatterned. In one embodiment, the first layer is an organic active layer in an electronic device. In one embodiment, the organic active layer is a hole injection layer or a hole transport layer. - In an embodiment, the first layer is a photoinitiator layer. In one embodiment, the first layer is a photoinitiator layer on the organic active layer in the electronic device. The first layer can be formed by any deposition technique including vapor deposition techniques, liquid phase beta deposition techniques, and thermal transfer techniques. In one embodiment, the first layer is deposited by liquid deposition techniques followed by drying. In this case, the first material is dissolved or dispersed in the liquid medium. The liquid deposition method can be continuous or discontinuous. Continuous liquid deposition techniques include, but are not limited to, spin coating, roll coating, curtain coating, dip coating, slot extrusion coating, spray coating, and continuous nozzle coating. Discontinuous liquid deposition techniques include, but are not limited to, ink jet printing, gravure printing, flexographic printing, and screen printing. In the first embodiment, the first layer was deposited by continuous liquid deposition techniques. The drying step can be carried out at room temperature or at elevated temperatures as long as the first material and any underlying materials are not damaged. The first layer is then processed with PCSA. This treatment can be carried out simultaneously with or after the formation of the first layer. In one embodiment, the PCSA treatment is performed simultaneously with the formation of the first organic active layer. The step of treating the first layer comprises depositing pcs a on the first layer. In one embodiment, PCSA is added to the liquid composition used to form the first layer. When the deposited composition is dried to form a crucible, sufficient PCSA is present at the air interface (i.e., the top surface) of the first layer 135696.doc -25.200933951 to reduce the surface energy of the system. In one embodiment, 'PCSA spontaneously migrates to the upper surface of the first organic active layer. In one embodiment, the PCSA process is performed after the formation of the first layer. In one embodiment, the PCSA is applied over a separate layer that is in direct contact with the first layer. : In one embodiment, 'PCSA' is applied without adding it to the solvent. In one embodiment, 'PCSA is applied by vapor deposition. ® In one embodiment, PCSA is applied by condensation. If PCSA is applied by condensation from the gas phase and the surface temperature is too high during vapor condensation, PCS A can migrate into the pores or free volume of the surface of the organic substrate. In some embodiments, the organic substrate is maintained at a temperature below the glass transition temperature or melting temperature of the substrate material. The temperature can be maintained by any known technique, such as placing the first layer on a surface that is cooled by a flowing liquid or gas. ❷ In one embodiment, PCSA is applied to the temporary support prior to the condensation step to form a uniform coating of PCS A. It can be achieved by any deposition method, including liquid deposition, vapor deposition, and heat transfer. In one embodiment - PCS A is deposited on a temporary support by continuous liquid deposition techniques. The choice of liquid medium used to deposit PCSA depends on the exact nature of the PCSA itself. Examples of liquid media include, but are not limited to, perfluorooctane, isopropyl alcohol, trifluoromethane, styrene, trifluoroethane, and hexafluoroxylene. In one embodiment, the material is deposited by spin coating. The coated temporary support is then used as a heating source to form steam for the condensation step. 135696.doc -26 - 200933951 The application of PCSA can be achieved by continuous or batch methods. For example, in the batch process, one or more devices will be simultaneously coated with pcSA and subsequently exposed to the radiation source. In a continuous process, a device transported on a belt or other conveyor will pass through a platform as it is sequentially coated by pCSA, and then continue through a platform where it is sequentially exposed to Korean source. Portions of the process may be continuous, and additional portions of the process may be batchwise. In one embodiment, the PCSA is liquid at room temperature and is applied to the first layer by liquid phase deposition. The liquid PCSA can form a film or it can be adsorbed or adsorbed on the surface of the first layer. In one embodiment, the liquid pcsA is cooled to a temperature below its melting point to form a second layer on the first layer. In one embodiment, the PCSA is not liquid at room temperature and is heated to a temperature above its dazzle, deposited on the first layer and cooled to room temperature to form a second layer on the first layer. For liquid phase deposition, any of the methods described above can be used. In one embodiment, PCSA is deposited from the second liquid composition. The liquid deposition method as described above may be continuous or discontinuous. In one embodiment, the PCSA liquid composition is deposited using continuous liquid deposition. The choice of the liquid medium used to deposit the pCSA2 depends on the exact nature of the PCSA material itself. After PCSA treatment, the PCSA is exposed to radiation. The type of radiation used will depend on the sensitivity of the PCS A as described above. The exposure is carried out in a pattern. The term "patterned" as used herein means that only selected portions of the material or layer are exposed. Exposure to the pattern can be achieved using any known imaging technique. In one embodiment, the pattern is achieved by exposure through a mask. In one embodiment, the pattern is achieved by exposing only selected portions to the grating laser. Exposure 135696.doc -27- 200933951 The exposure time can be visualized using the specific chemical basis of the PCSA. In the range of seconds to minutes. When using a laser, depending on the power of the laser, the exposure time for each area is much shorter, depending on the sensitivity of the machine. The exposure step can be carried out in air or in an inert atmosphere.

In an embodiment, the light projecting system is selected from the group consisting of ultraviolet light ray (-39 〇 nm), visible light ray (39G_77G nm), infrared radiation (77 () _1 () 6 nm), and combinations thereof. Includes simultaneous and continuous processing. In one embodiment, the radiation is farther than ν (2(Η)·3(Η) nm). In another embodiment, the ultraviolet radiation has a wavelength between 300 and 400 nm. In another embodiment, the radiation has a wavelength between 4 450 and 450 nm. In an embodiment, the radiation is thermal radiation. In one embodiment, exposure to the radiation is performed by heating. The temperature and duration of the heating step cause at least one physical property of the PCSA to be altered without damaging any underlying layers of the luminescent region. In one embodiment, the heating temperature is below 25 °C. In one embodiment, the heating temperature is below 15 〇〇c. In one embodiment, the radiation is ultraviolet radiation or visible radiation. In one embodiment, the radiation is applied in a pattern to produce an exposed area of PCSA and an unexposed area of PCS A. In one embodiment, the radiation is far UV radiation having a wavelength of 2 〇〇 3 〇〇 nm. In another embodiment, the ultraviolet radiation has a wavelength between 300 and 400 nm. In another embodiment, the radiation has a wavelength between 400 and 450 nm. After exposure to radiation in a pattern, PCSA was treated to remove PCSA from the unexposed areas of the layer. The treatment of exposure to radiation in a pattern and removal of PCSA from unexposed areas is well known in photoresist technology. In one embodiment, exposing PCSA to radiation causes a decrease in the cold solution or dispersibility of PCSA in the solvent 135696.doc -28 - 200933951. The wet development process can be performed after the exposure step. This treatment typically involves washing with a solvent that dissolves, disperses or lifts off the unexposed areas of the PCSA. In an embodiment, exposing the PCSA to a shot produces a reaction that reduces the volatility in the exposed zone. After exposure in a pattern, thermal development treatment can then be carried out to volatilize PCSA from the unexposed areas. The treatment involves heating to a temperature above the volatilization or sublimation temperature of the unexposed material and below the heat curable temperature of the material. For example, for a polymerizable monomer, the material is heated at a temperature above the sublimation level and below the thermal polymerization temperature. It will be appreciated that PCSA materials having a thermal reactivity temperature near or below the volatilization temperature may not be developed in this manner. In one embodiment, exposing the PCSA to radiation causes a temperature change in the material that melts, softens, or flows. Dry development can be carried out after exposure. The dry development process can include contacting the outermost surface of the component with the adsorption surface to absorb or carry away the softer portion via capillary action. This dry development can be carried out at a high temperature as long as it does not further affect the characteristics of the initially unexposed area. In one embodiment, exposing the PCSA to radiation causes the volatility of the pcSA material to decrease. After treatment with PCSA, after exposure to radiation and development, the first layer in the unexposed area where p(:SA has been removed has a higher surface energy than the area of the remaining photocured PCSA. One way to determine relative surface energy is to compare The contact angle of a given liquid on the first organic active layer before and after treatment with PCSA. The term 'contact angle' as used herein means the angle φ shown in the figure 。. For liquid medium droplets 135696. Doc -29- 200933951 and the 3' angle φ is defined by the intersection of the surface plane and the line from the outer edge of the droplet to the surface. In addition, after the droplet is applied, the equilibrium position is measured on the surface, and the angle Φ is measured. That is, "static contact angle". Many manufacturers manufacture equipment capable of measuring contact angles. In one implementation, the contact angle of the photocured pcs_benzoic puzzle described in this article exceeds 6〇. In some embodiments, more than 70. In certain embodiments, the 'lower contact angle is acceptable and the contact angle with the benzo of the beetle is between 30 and 60.

第二 Next, apply a second layer to the untreated area of the first layer. The first layer can be applied by any deposition technique. In an embodiment, the second layer is applied by a liquid deposition technique. In this case, the liquid composition comprises a second material which is dissolved or dispersed in a liquid medium, applied to the untreated zone of the first layer and dried to form a second layer. A liquid composition having a surface energy higher than that of the treated layer of the first layer (photocured PCS A) but having a surface energy substantially the same as or less than the surface of the untreated first layer is selected. Thus, the liquid composition will wet the first layer in the unexposed areas of the PCSA that has been removed by development, but will be repelled by the treated first layer in the exposed area. The liquid can spread over the treated first zone but it will dewet. In one embodiment 'PCSA is patterned and the second layer is applied using continuous liquid phase deposition techniques. In one embodiment, the second layer is applied using a discontinuous liquid phase deposition technique. In one embodiment, the first layer is applied to the liquid enclosure structure. It may be necessary to use a structure that is not sufficient to completely enclose, but still allows adjustment of the thickness uniformity of the printed layer. In this case, it may be necessary to control the thickness of the thickness adjustment knot 135696.doc 30- 200933951 to provide a package for both uniformity. It is then necessary to be able to adjust the contact angle of the emissive ink. Most surface treatments used for enclosures (such as CF4 plasma) do not provide control of this level. In an embodiment, the first layer is applied to a so-called bank structure. The bank structure is usually formed of a photoresist, an organic material (e.g., polyimide) or an inorganic material (oxide, nitride, and the like). The bank structure can be used to prevent the color mixing of the first layer of the package & body type; and/or to improve the thickness uniformity of the first "drying from its liquid form; and / or to protect the lower layer of material Soak it out of contact with liquids. The underlying features can include conductive traces, gaps between conductive traces, thin film transistors, electrodes, and the like. It is often desirable to form regions of different surface energies on the bank structure to achieve two or more purposes (e.g., to prevent color mixing and also to improve thickness uniformity). A method is to provide a bank having a plurality of layers (each layer having a different surface energy): a structure. A more cost-effective way to achieve this surface energy adjustment is to control the surface energy via the f-section to cure the PCSA radiation. The cured radiation modulating section can be in the form of an energy dose (power multiplied by the exposure time) or by exposing the PCSA (e.g., via a halftone density mask exposure) via a reticle pattern that simulates different surface energies. In one embodiment of the method provided herein, the first and second layers are a hydrophobic active layer. Forming a first organic active layer on the first electrode, treating the first organic active layer with the photocurable surface active composition to reduce the surface energy of the layer, and forming a second on the treated first organic active layer Organic active layer. In the embodiment, the first organic active layer is formed by liquid-depositing a liquid composition comprising a first organic active material and a liquid medium of 135696.doc -31 - 200933951. The liquid composition is deposited on the first electrode and then dried to form a layer. In one embodiment, the first organic active layer is formed by continuous liquid phase deposition. These methods can result in higher yields and lower equipment costs. In one embodiment, PCSA is deposited from the second liquid composition. As described above - the liquid deposition method may be continuous or discontinuous. In one embodiment, the PCSA liquid composition is deposited using a continuous liquid deposition process. • When depositing PCSA in the form of a separate layer, the thickness of the photocured PCSA may depend on the end use of the material. In certain embodiments, the thickness of the photocured PCSA layer is less than 1 Å. In certain embodiments, the thickness is less than 10 A. In certain embodiments, the photocured pcsA layer has a thickness of at least 100 A. In certain embodiments, the thickness is in the range of 100-3000 A; in certain embodiments, it is in the range of 1000-2000 A. 4. Organic Electronic Devices This method will be further described in terms of its use in electronic devices, but it is not limited to such applications. 2 is an exemplary electronic device that is an organic light emitting diode (OLED) display including at least two organic active layers between two electrical contact layers. The electronic device 100 includes one or more layers 12 and 13 to facilitate the injection of holes from the anode layer 110 into the photoactive layer 14 . In general, when two layers are present, the layer 12 adjacent to the anode is referred to as a hole injection layer or a buffer layer. The layer 130 adjacent to the photoactive layer is referred to as a hole transport layer. An optional electron transport layer 150 is located between the photoactive layer 140 and the cathode layer 160. The organic layers 120 to 150 are individually and collectively referred to as the organic active layer of the device. Depending on the application of the device, 135696.doc -32- 200933951 The photoactive layer 140 may be a light-emitting layer activated by an applied voltage (such as in a light-emitting diode or in a light-emitting electrochemical cell) in the presence or absence There is a layer of material that reacts to radiant energy and produces a signal when an applied bias voltage (such as in a photodetector) is present. The system, drive method and utility mode of the device are not limited. For multi-color devices, photoactive layer 140 is comprised of different regions of at least three different colors. Areas of different colors can be formed by printing separate colored regions. Alternatively, it can be achieved by forming an entire layer and doping different regions of the layer with emissive materials of different colors. This method is described in, for example, U.S. Patent Application Serial No. 2004-0094768. In an embodiment, the novel method described herein can be used to apply an organic layer (second layer) to the electrode layer (first layer). In one embodiment, the first layer is the anode 110 and the second layer is the buffer layer 120. In certain embodiments, the novel methods described herein can be used with any continuous organic layer pair in a device where the second layer will be enclosed in a particular area. A method of fabricating an organic electronic device comprising a first organic active layer and a second organic active layer on an electrode comprises: forming a first organic layer having a first surface energy on an electrode; and comprising a group selected from the group consisting of: The photocurable surface active composition of the material treats the first layer: fluorinated vinegar of α,β-unsaturated polybasic acid, fluorinated quinone imine of α,β-unsaturated polybasic acid, and combinations thereof; The surface active composition is exposed to radiation in a pattern to produce an exposed area and an unexposed area; the photocurable surface active composition is developed to remove the photocurable surface active composition from the unexposed area, resulting in an unexposed area having no The processed portion 135696.doc -33- 200933951 and having a treated portion of the first organic active layer in the exposed region, wherein the treated portion has a second surface energy lower than the first surface energy; and the first organic active layer A second organic layer is formed on the untreated portion.

In certain embodiments of the new method, the first and second organic layers are organic active layers in the device. In one embodiment of the new method, the second organic layer is the photoactive layer 140'. The first organic active layer is the device layer applied immediately prior to layer 140. In many cases, the device is initially constructed with an anode layer. When the hole transport layer 130 is present, the pattern pcSA process is applied to the layer 13A, and then the photoactive layer 140 is applied. The pcSA process is applied to layer 120 when layer 13 is absent. In the case where the device is initially constructed with a cathode, PCSA treatment is applied to the electrode transport layer 15A, followed by application of the photoactive layer 140°. In one embodiment of the new method, the first organic layer comprises a photoinitiator and a second The organic layer is a photoactive layer. In one embodiment of the new method, the second organic layer is the hole transport layer 130 and the first organic layer is the device layer applied immediately before the layer 13〇. In an embodiment where the apparatus is initially constructed with an anode layer, PCSA processing is applied to the buffer layer 120, followed by application of the hole transport layer 130. In an embodiment, the anode 11 turns are formed in a parallel stripe pattern. Alternatively, the electrodes can be an array of patterned structures having planar shapes such as squares, rectangles, circles, triangles, ellipses, and the like. The buffer layer 120 and, optionally, the hole transport layer 130 are formed on the anode 11A in a continuous layer. The PCSA process is applied to layer 130 (if present) or layer 120 (when layer 130 is not present). The PCSA is exposed in a pattern exposed between the anode material and the outer edge of the anode material. The layers in the device can be made of any material known to be suitable for the layers. A support or substrate (not shown) that can be adjacent to the anode or cathode layer 150 is included. Most often, the support is adjacent to the anode layer 11A. The support can be a flexible or rigid, organic or inorganic support. In general, a glass or flexible organic film is used as a support. The anode layer 11A is an electrode which is more effective than the cathode layer 160 in terms of injection holes. The anode may comprise a material comprising a metal, a mixed metal, an alloy, a metal oxide or a mixed oxide. Suitable materials include mixed oxides of Group 2 elements (i.e., Be, Mg, Ca, Sr, Ba), Group 11 elements, Group 4, 5 and 6 elements, and Group 8-10 transition elements. If the anode layer 110 is to be made transparent, a mixed oxide of Groups 12, 13 and 14 elements such as indium tin oxide may be used. The phrase "mixed oxide" as used herein refers to an oxide having two or more different cations selected from Group 2 elements or Group 12, 13 or 14 elements. Some non-limiting specific examples of the anode layer 11 〇 material include, but are not limited to, indium tin oxide ("ITO"), indium zinc oxide, aluminum oxide tin, aluminum oxide, gold, silver, copper, and nickel. Organic materials such as polyaniline, polythiophene or polypylon may also be included. The anode layer 110 may be formed by chemical or physical vapor deposition or spin casting. Chemical vapor deposition may be plasma enhanced chemical vapor deposition ( "PECVD" or metal organic chemical vapor deposition ("M〇CVD"). Physical vapor deposition can include all forms of sputtering, including ion beam sputtering, as well as electron beam evaporation and resistance evaporation. Specific forms of vapor deposition include rf magnetron sputtering and inductively coupled plasma physical vapor deposition 135696.doc -35. 200933951. These deposition techniques are common in semiconductor fabrication techniques, and the anode layer 11 is The pattern needs to be changed during the lithography operation. The layers can be pressed, for example, in the first case.

A patterned mask or anti-surge is placed on the structure, followed by application of the first = = = material to form a pattern. Alternatively, the layers can be applied in a monolithic manner: (also known as blanket deposition) and subsequently patterned using, for example, patterned anti-layer and wet chemical or dry etching techniques. Other patterning methods well known in the art can also be used. When the electronic device is located within the array, the anode layer 110 is typically formed as substantially parallel strips of length extending in substantially the same direction. The buffer layer 120 serves to facilitate the injection of holes into the photoactive layer and to smooth the surface of the anode to prevent short circuits in the device. The buffer layer is typically formed from a polymeric material that is typically doped with a protic acid, such as polyaniline (PANI) or poly(ethylenedioxythiophene (PEI) OT). The protonic acid can be, for example, poly(styrenesulfonic acid), poly(2- acrylamido-2-methyl-1-propionic acid), and the like. The buffer layer j 20 can comprise a charge transport compound. And analogs thereof, such as copper ugly and tetrathiafulvalo_tetracyanoquinone dimethane system (TTF-TCNQ). In one embodiment, the buffer layer 120 is formed from a dispersion of a conductive polymer and a colloid-forming polymeric acid. Such materials are described, for example, in published U.S. Patent Application Nos. 2004-0102577 and 2004-0127637. The buffer layer 120 can be applied by any deposition technique. In one embodiment, the buffer layer is applied by solution deposition as described above. In one embodiment, the buffer layer is applied by continuous solution deposition. Examples of hole transport materials for the optional layer 130 are outlined (for example) in Y. 135696.doc • 36- 200933951

Wang Kirk Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, pp. 837-860, 1996. Both hole transport molecules and polymers can be used. Common hole transport molecules include (but are not limited to): 4,4',4"-parameter (N,N-diphenylamino)-triphenylamine (TDATA); 4,4',4"-parameter (N -3-methylphenyl-N-phenylamino)triphenylamine (MTDATA); N,N'-diphenylhydrazine

-N,N'-bis(3-methylphenyl)-[1, fluorene-biphenyl]-4,4'-diamine (TPD); 1,1-bis[(di-4-methylphenyl) Amino)phenyl]cyclohexane (TAPC); Ν,Ν'-bis(4-methylphenyl)-indole, Ν'-bis(4-ethylphenyldimethyl)biphenyl]_ 4 , 4,-diamine (£丁?0); 肆(3-methylphenyl)-team>1,,1^-2,5-phenylenediamine (PDA); α-phenyl-4 -Ν, Ν-diphenylaminostyrene (TPS); p-(diethylamino)benzaldehyde diphenyl hydrazine (DEH); triphenylamine (ΤΡΑ); bis[4-(Ν,Ν-diethylamino -2•methylphenyl](4-rodylphenyl)methane (ΜΡΜΡ); 1-phenyl·3-[p-(diethylamino)styryl]·5-[p-(diethylamine) Phenyl]pyrazoline (ppR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB); N,N,N',N'-肆( 4-methylphenylbiphenyl) 4 4, diamine (TTB); N,N'-bis(naphthalen-1-yl-(phenyl)benzidine (α_ΝρΒ); and porphyrin-based compounds such as copper ruthenium Cyanine. Common hole transport polymers include, but are not limited to, polyethyl salium, (phenylmethyl) polysulfide, poly(dioxy porphin), polyaniline and poly Alternatively, a hole transport polymer can be obtained by doping a hole in a polymer such as polystyrene and polycarbonate, such as the above-mentioned hole transport molecules. In an embodiment, the hole: the transport material comprises a crosslinkable oligomeric material or a polymeric material. After forming the hole transport layer, the material is disposed of by light treatment. In some embodiments, the radiation is heat. Radiation 135696.doc -37- 200933951 The hole transport layer 13 can be applied by any deposition technique. In one embodiment, the 'hole transport layer is applied by solution deposition as described above. In one embodiment The hole transport layer is applied by continuous solution deposition. Any organic electroluminescence ("EL") material can be used in the photoactive layer 140. • Including, but not limited to, small molecule organic fluorescent compounds, fluorescent And phosphorescent-metal complexes, co-polymers, and mixtures thereof. Examples of fluorescent compounds include, but are not limited to, ruthenium, osmium, ruthenium, coumarin, derivatives thereof, and mixtures thereof. Examples of things include (but are not limited to a metal chelate 咢 octyl compound, such as ginseng (8-hydroxy decanoate) aluminum (Alq 3 ); a ring metal ruthenium and an electroluminescent compound such as, for example, petrov et al., U.S. Patent No. 6,670,645 and disclosure a complex of hydrazine with a phenylpyridine, a styrylquinoline or a stupidylpyridinary ligand disclosed in PCT Application Nos. 3/〇63555 and w〇2004/016710; and in, for example, published Organometallic complexes described in PCT Application Nos. WO/03/008424, WO 03/091688, and WO 03/040257; and mixtures thereof. An electroluminescent emissive layer comprising a charge-carrying host material and a gold-based complex is described in U.S. Patent No. 6,303,238 to Thompson et al., and to PCT in the PCT issued by Burrows and Thompson. WO 00/70655 and WO 01/41512 Described in. Examples of conjugated polymers include, but are not limited to, poly(phenylene vinyl), polyfluorene, poly(spiropyrene), polythiophene, poly(p-phenylene), copolymers thereof, and mixtures thereof. The photoactive layer 140 can be applied by any deposition technique. In one embodiment the <photoactive layer is applied by solution deposition as described above. In one embodiment, the photoactive layer is applied by continuous solution deposition. Optional layer 150 can be used to facilitate electron injection/transport and can also act as a confinement layer 135696.doc-38-200933951 to prevent quenching reactions on the layer interface. More specifically, layer 150 may increase electron mobility and reduce the likelihood of quenching reactions in the event that layers 140 and 160 would otherwise be in direct contact. Examples of optional layers of materials include, but are not limited to, metal chelate a compound of oxin (such as Alq3 or its analogs); a compound based on morpholine (such as 2,9-dimercapto-4,7-diphenyl- l,l- phenanthroline) ("DDPA"), 4,7-diphenyl-1,10-morpholine ("DPA" or its analogs); azole: a compound such as 2-(4-biphenyl)-5-(4 -T-butylphenyl)-1,3,4-oxa•disal ("PBD" or its analogs), 3_(4_biphenyl)_4_phenyl_5_(4-third Butylphenyl h1,2〆-triazole ("TAZ" or its analogs); other analogous compounds or any one or more combinations thereof. Alternatively, optional layer 150 can be an inorganic layer 'and contain BaO, LiF, Li20 or its analog. Cathode 160 is an electrode that is particularly effective for injecting electrons or negative charge carriers. Cathode layer 160 can have a lower work function than the first electrical contact layer (in this case, anode layer 110). Any metal or non Metal. In one embodiment, the term "lower work function" means a material having a work function φ of no more than about 4 4 eV. In one embodiment, a higher work function means at least A material for a work function of about 4.4 eV. The material for the cathode layer may be selected from Group 1 alkali metals (e.g., Li, Na, K, Rb, Cs), Group 2 metals (e.g., Mg, Ca, Ba, or the like). , a Group 12 metal, a steel element (such as Ce, Sm, Eu, or the like), and a lanthanide (such as Th, U or the like). Also used are materials such as aluminum, indium, and antimony. Materials of Combination. Specific non-limiting examples of materials for the cathode layer 16〇 include, but are not limited to, ruthenium, lithium, osmium, planer, ruthenium, osmium, yttrium, iridium, phenanthrene, and alloys thereof, and combinations thereof. Doc • 39· 200933951 Cathode layer 160 is typically formed by chemical or physical vapor deposition. In other embodiments, additional layers may be present within the organic electronic device. The device is fabricated on the anode side, as described herein. The PCSA processing step of the new method described can be formed in the buffer layer 12 after the anode 110 is formed. After the formation, after the hole transport layer 130, or any combination thereof, when the device is initially fabricated on the drain side, the new method described herein can be formed after the cathode 160 is formed in eight processes. The transport layer 15, or any combination thereof, may have any suitable thickness. The inorganic anode layer m typically does not exceed about 50 nm, such as about nm; the buffer layer 12 and the hole transport layer 130 are each typically Not more than about 25 〇 nm, for example about 5 〇 2 〇〇 'photoactive layer i4 〇 usually does not exceed about 1000 nm, for example about 5 〇 8 〇 150 usually does not exceed about 1 〇〇 nm, for example about 2 〇 8 〇 Claw; nm; optional layer and cathode layer 160 typically no more than about 100 nm, such as about _5 〇 nm. If the anode layer or the cathode layer 160 is required to transmit at least some of the light 'the thickness of the layer may not exceed about 100 nm. The following examples will be described in the following examples, and the examples do not limit the towel. Please refer to the invention of the invention described in the patent scope. Example 1 Example 1 demonstrates the high surface energy of an interlayer film formed from PCSA as described herein on the first layer of the hole transport polymer. Wei Weishuang (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) anti-butanic acid W PCM·1"). The synthesis of this material is given in Example 12. 135696.doc 200933951 The hole transport polymer is a crosslinkable copolymer of triphenylamine, dioctylfluorene and distyrylfluorene ("HT-1"). A 30 mm glass test piece was spin-coated with a 0.35 wt/vol0/〇 solution of HT-1 in toluene; the resulting film was then cured at 275 ° C for 30 min. Next, PCSA-1 was spin-coated (600 rpm, 60 sec) on a 5 wt/vol% solution in perfluorooctane on the surface of the hole transport layer. The resulting test piece was then exposed to a 248 J/cm2 exposure dose of UV light; it was then placed on a hot plate and baked at 175 ° C for 120 sec, then cooled to room temperature. The wafer surface was washed with several milliliters of perfluorooctane and dried at room temperature. The contact angle was measured on the surface using anisole to obtain a 65-69° advancing contact angle and a 48-51° receding contact angle. When a separate HT-1 film was washed with perfluorooctane and dried, the contact angle measured using phenyl ether was about 15. , much smaller than the layer treated with PCSA-1. Example 2 This example shows that comparative radiation-sensitive materials are commercially available from Sigma-Aldrich Co. (St. Louis, MO) 3,3,4,4,5,5,6,6,7,7,8,8 ,9,9,10,10,11,11,12,12,12-^ 廿-Fluorodecyl acrylate (h2c=chco2ch2ch2(cf2)9cf3) ("PDEA") The evaporation behavior of PCSA as described. Samples PCSA-1 and PDEA (comparative) were placed in an aluminum pan and evaporated in a Q600 TGA (TA Instruments, Delaware, USA) at 25t:. The flow rate of the purge gas is 100 ml/min. The evaporation rate is as follows: PCSA-1: 0.009 μg/min PDEA (comparative): 0.8 μg/min 135696.doc -41 - 200933951 It shows that PCS A-1 evaporates much more slowly at ambient temperature, providing processing more time. Example 3 This example illustrates the PCSA treatment performed simultaneously with the formation of the first layer. Solution A: 100% HT-1 solution B: 40% PCSA-1/60% HT-1; all solutions were prepared in toluene at 0.33% (solid weight/solvent volume). These solutions were spin-coated on a borosilicate glass test piece to obtain a dried coating of about 20 nm thick φ. The test piece coated with the two solutions was exposed to ultraviolet radiation of a wavelength of 248 nm at a dose of 2.7 J/cm2. The development step of PCSA was carried out by baking the test piece in an oven at 275 ° C for 30 minutes under a nitrogen atmosphere. It removes PCSA-1 in the unexposed zone and thermally crosslinks with HT-1. The contact angle was measured on the resulting film using phenyl ether ether as the test fluid with an uncertainty of +/- 2 degrees: Exposure = 0 J/cm2 Contact angle on the film formed from solution A: 7 degrees formed from solution B Contact angle on the film: 9 degree exposure: about 2.7 J/cm2 Contact angle on film formed by solution A: contact angle on film formed by solution B at 8 degrees: 32 degrees in unexposed sample and exposed to 2.7 There was no significant difference between the films formed by solution A of J/cm2. The film containing PCSA-1 has a significantly higher contact angle after exposure. It demonstrates the addition of PCSA-1 to HT-1 to provide a film that exhibits a permanent change in surface energy upon exposure to radiation. The PCSA can be removed from areas that are not exposed to radiation 135696.doc -42- 200933951. EXAMPLE 4 This example shows a maleic acid-substituted fluoroalkyl alcohol maleic acid vinegar, bis(3,3,4,4,6,6,7,7,8,8,8-undefluoro -5-Sideoxy-octyl) maleate ("PCSA-2"). 2

F2 f2 H〇^/c, (r0, c, c, CF + f2 f2 PPVE-OH

Add ppvE_〇H (17 8 g, 〇〇54 mol), toluene (1 〇〇 mL), MAn to a 250 mL 4-neck round bottom flask equipped with a stir bar, thermocouple, Dean_Stark separator and condenser. (2 6 g , 〇〇27 m〇1) and p-toluenesulfonic acid (〇.50 g, 0.0027 m〇l) gave a colorless mixture. The mixture was heated to reflux to make the mixture homogeneous and maintained overnight. from

Some water is removed from the Stark separator. After refluxing for two days, by using ethyl acetate

(50 mL) was diluted and washed with saturated aqueous sodium bicarbonate (35 mL) to gradually complete. It was then washed with a saturated aqueous solution of NaCI (35 mL). The combined aqueous washes were extracted with ethyl acetate (50 mL) and the combined organic portions were dried over MgSO. The dried organic layer was filtered and taken at 35. The solvent was removed under reduced pressure to give a creamy white oil. lH, threshold and "F nmr are not too large. The product is classified as the desired product and TGA indicates that all products are volatile. Example 5 This example shows a non-cavity transport layer on a double layer (3,3 4,4,6,6,7,7 8,8,8_11 135696.doc •43- 200933951 fluoro-5-sideoxy Contact angle measurement of the interlayer film formed by _octyl) maleate. The hole transport layer is a crosslinkable copolymer of triphenylamine, dioctylfluorene and diphenylvinylguanidine prepared as in the example. A 5 Wt/vol% solution of PCSA-2 from Example 4 in perfluorooctane was then spin coated (12 rpm, 60 sec) onto the surface of the hole transport layer. The resulting test piece was then exposed to ultraviolet light at 248 nm - wavelength for a period of 15 minutes, resulting in an exposure dose of 1.35 J/cm2. It was then placed on a hot plate and baked at 175 ° C for 300 sec, then cooled to room temperature. Using the R〇mbHart contact angle goniometer, the advancing contact angle was measured on this surface using 62.72. The result. When the individual HT-1 film was washed with perfluorooctane and dried, the contact angle measured using anisole was about 15. , much smaller than the treated layer. Example 6 This example shows the cis-succinate-bis(3,3,5,5,6,6,7,7,8,8,8-fluoroindolyl) cis-butane Synthesis of enedionate ("PCSΑ-3").

F2 f2 f2 2 HO^x^Cv^C"C-"C"CF3 + . F2

C4IVDF-OH Add C4IVDF-OH (17.8 g, 0.054 mol), toluene (100 mL), MAn to a 250 mL 4-neck round bottom flask equipped with a stir bar, thermocouple, Dean-Stark separator and condenser. 2.6 g, 0.027 mol) and p-toluenesulfonic acid (0.50 g, 0.0027 mol) gave a colorless mixture. The mixture was heated to 135696.doc -44 - 200933951 to reflux to allow the mixture to homogenize and continue to heat overnight. Remove some water from the Dean Stark knife. After two days of refluxing, the reaction was gradually completed by diluting with EtOAc (50 mL) and washing with saturated aqueous sodium hydrogen carbonate (3 EtOAc). It was then washed with a saturated aqueous solution of NaCI (35 mL). The combined aqueous washes were extracted with ethyl acetate (5 mL) and the combined organic <RTI ID=0.0> Filter the dried organic layer

And at 35 ° C

The solvent was removed under reduced pressure to give a pale yellow oil. h, 13C and 19F • means that most of the product is the desired product and TGA indicates that all products are swellable. Example 7 This example shows a film formed on a hole transport layer from bis(3,3,5,5,6,6,7,7,8,8 8-undecfluorooctyl) maleate. Contact angle measurement. The hole transport layer is a crosslinkable copolymer of triphenylamine, dioctylfluorene and diphenylethylene ruthenium ("HT-1") prepared as in the example. Next, a 5 wt/v 〇 1% solution of PCSA-3 from Example 6 in perfluorooctane was spin coated (12 rpm, 6 〇 φ SeC) on the surface of the hole transport layer. The resulting test piece was then exposed to ultraviolet light at a wavelength of 248 nm for a period of 15 minutes, resulting in an exposure dose of 丨35 J/cm2. It is then placed on a hot plate and at 175. (: Bake for 300 sec, - then cool to room temperature. Use R〇m0-Hart contact angle goniometer on this surface to measure the advancing contact angle with anisole to get 3丨_35. When HT-1 alone was washed with perfluorooctane and dried, the contact angle measured using anisole was about 15. It was much smaller than the treated layer. Example 8 JL^a N-4,4, 5,5,6,6,7,7,8,8,9,9,10,10,11,11,11 - I35696.doc -45- 200933951 Heptafluoroundecyl-p-butyleneimine ("PCSA-4") Measurement of contact angle on the formed film. PCSA-4 was purchased from Fluka Chemical and Aldrich Chemical, St, Louis, MO, [S52527-body 3].

The hole transport layer was a crosslinkable copolymer of triphenylamine, dioctyl and diphenylethylene ruthenium prepared as in Example 1 ("HT-1"). Then, a saturated solution of PCSA-4 in isopropyl alcohol was spin-coated (600 rpm, 60 sec) on the surface of the hole transport layer, and then the obtained test piece was exposed to ultraviolet light at a wavelength of 248 nm for 3 minutes, resulting in a period of 3 minutes. 2.7 J/cm2 exposure dose. It was then placed on a hot plate and baked at 175 t: for 3 sec, then cooled to room temperature. The R〇m0 Hart contact angle goniometer was used on this surface to measure the advance contact angle using the benzotribe to obtain 77.8G. The result. When the individual (iv) film was washed with whole gas and dried, the contact angle measured using phenyl ether was about 15. , much smaller than the treated layer.实例 Example 9 This example shows a substituted fluoroalkyl alcohol of itaconate-bis(3'3'4'4'5'5,6,6,7,7,8,8,8-trifluoro Synthesis of octyl) itaconate ("?.8-8-5"].

135696.doc • 46 · 200933951

F2 f2 f2 K Fz F2 X° f2 f2 0^\cO, c 乂, c, CF3 f2 f2 f2 Add 1 398 醯 ( (19.1398, 〇 114 mol) (Aldrich) to 3 [3 neck round bottom flask, 3 , 3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl alcohol (83.·462 g' 0.229 mol) and THF (130 mL). The mixture was cooled in an ice bath. DiPEA (29.59 g, 0.229 mol) was added dropwise to the cooled solution via an addition funnel to give a dark brown color. The mixture was allowed to pass overnight at room temperature. The ammonium salt was filtered off and the filtrate was concentrated under reduced pressure to remove solvent. The ice color product was placed in the sublimation unit and then carefully emptied until the foaming ceased. It was then sublimed at 60 ° C until it was cooled with liquid nitrogen to a cold finger to give a white solid. The white solid collected on the cold finger was rinsed with acetone to a vial and then dried under vacuum. The total product collected was 18_46 g or 20%. iH NMR revealed the desired product with very small amounts of impurities. Example 10 +2

X CI· This example shows the formation of a double (3,3,4,4,5,5,6,6,7,7,8,8 8_ thirteen octyl) itaconate on the hole transport layer Contact angle measurement on the film.

The electro/co-transporter layer was a triphenylamine, dioctylfluorene and distyryl-based crosslinkable copolymer prepared as in Example 1 to prepare a crude 135696.doc-47·200933951 PCSA-5 from Example 9. A solution of fluorooctane (3% (wt/vol)) and sublimed PCSA·5 (in isopropanol) (3% (wt/vol)). The solution was then spin coated (1200 rpm, 60 sec) onto the surface of two separate hole transport layers. The test piece with the crude material was then exposed to 248 nm, 2.7 J/Cm2 dose of UV light (30 min), followed by baking at 65 °C for 2 min and bake at i3 〇 °c for 2 min. The test piece with the sublimation material was then exposed to a 365 nm UV lamp; the UV was applied for 60 seconds (about 2.6 J/cm2), followed by baking at 65 °C for 2 min and baking at 130 °C for 2 min. The advancing contact angle was measured on the surface of the crucible using a R〇m6-Hart contact angle goniometer, which yielded 45-57 for the crude product exposed using short-wavelength radiation. As a result, and for the sublimation product using long-wavelength radiation exposure, 28-31 is obtained. The result. The contact angles of both groups are generally higher than the contact angle of the untreated surface. Example 11 This example illustrates the bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) maleate ("PCSA- 6") synthesis. © 111, out, 21^2^ perfluoro-1-octanol (8 1 £11^11) (36.2 g, 99.4 mmol) placed in a 250 ml flask under nitrogen and with cis-butene The anhydride (4〇6 • Mock '41.4 mmol) was treated with 'p-toluene monohydrate (0.78 g, 4.1 mmol). The mixture was stirred and heated to 113-115 ° under nitrogen (: a clear, colorless liquid was obtained. The mixture was maintained at 113-115. (:: 65 min. The reaction mixture was chromatographed on EtOAc (5 cm diameter and 19 cm length) to give 27.07 g (81%) of colorless oil. The oil solidified at room temperature and then dissolved. In a minimum amount (several milliliters) of ethyl acetate. 135696.doc -48- 200933951

The solution was diluted to approximately 40 ml of hexane to near the cloud point. The solution was allowed to cool in an ice bath and then inoculated with a previously synthesized solid product sample. The resulting crystalline solid was filtered, washed three times with hexanes, dried and then dried under high vacuum to afford 18.52 g (55% yield) of white solid. NMR (CDC13): δ (ppm): 6.29 (S, 2H), 4.50 (t, 4H), 2.53 (m 4H) 〇l9F NMR (CDC13): δ (ppm): -81.3 (m, 6F), - Li4.i (mj ; 4F), -122.3 (m, 4F), -123.3 (m, 4F), -124.0 (m5 4F), -126.6 (m, 4F) 〇Example 12 This example shows double (3,3 , 4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) fumarate (&quot;PCSA-1&quot;). 111, 111, 211, 211-perfluoro-1-octanol (8 1 (11' 丨〇 11) (38.32 g, 99.4 mmol) was placed in a 1 liter 3-neck flask under nitrogen and dissolved in 1861111 Dioxane in methane. The solution was treated with triethylamine (10.66 g, 105.3 mmol) and then cooled to 2 ° C in an ice bath. The solution was stirred and counter-butanized with helium (8 bismuth) 11) (8.05 g, 52.6 mmol) was treated in a solution of 42 1111 in a methane for 10 minutes. The mixture was allowed to warm (exotherm) to 10 ° C during the addition. The mixture was stirred for an additional 10 minutes in an ice bath. Then, it was allowed to warm to room temperature over 8 hours. The mixture was treated with water (300 ml) with stirring. The dioxane layer was separated 'washed once with water', dried over anhydrous magnesium sulfate, filtered and concentrated to give 38. Gram of brown solid. The solid was dissolved in a minimum of ethyl acetate and chromatographed on a silica gel column (5 cm diameter and 15 cm length) using 20% ethyl acetate in hexane to give 29.81 g (70%) Yellow solid. Dissolve the solid in warm toluene (25 ml) and pass through medium sintered glass 135696.doc -49· 200933951 The filtrate was allowed to stand at room temperature. 'The crystal formed at this time. The solid was taken out' to be washed with toluene, washed with hexane and air-dried to obtain 23.1 5 g of a pale yellow solid. Again from toluene (25 The crystals were recrystallized from ml. The solid was filtered off and washed with hexanes and dried to give 21.24 g of pale yellow color solid. Part (11.36 g) was dissolved in ethyl acetate and used in the home. 20 〇 / 〇 ethyl acetate on a silica gel column (5 cm diameter and 16 cm length) of the upper layer: 11.3 g of a pale yellow solid was obtained, which was recrystallized from toluene (20 ml) to give 7.67 g of pale pale yellow solid. Dissolved in warm toluene (15 ml) ® , treated with activated carbon and filtered through a medium fritted funnel. The filtrate was allowed to stand at room temperature. The obtained crystals were filtered, washed with benzene, washed with hexane, air dried and vacuum Drying gave 5.86 g of very pale yellow solid. iH NMR (CDC13): δ (ppm): 6.87 (s, 2H), 4.52 (t, 4H), 2.54 (m, 4H). 19F NMR (CDC13): δ (ppm) ): -81.3 (m, 6F), -113.9 (m, 4F), -122.3 (m, 4F), -123.3 (m, 4F), -124.0 (m, 4F), -126.6 (m, 4F). Example 13 This example shows an alternative synthesis of PCSA-1. 111, 111, 211, 211-perfluoro-1-octanol (into 1 (114 (; 11) (39.82 g, 1 〇9.4 mM) was placed in a 1 liter 3-neck flask under nitrogen and dissolved in 19〇1111 anhydrous THF. The solution was then cooled to 2 in an ice bath. 〇, and treated with a solution of Aldrich (8.05 g, 52.6 mmol) in 45 ml of anhydrous THF for 5 minutes. The clear, colorless solution was mixed in an ice bath for a few minutes. The solution was treated with diisopropylethylamine (14 7 g, U4 mmol) for a period of 2 minutes to give an instant dark brown mixture with suspended solids. The mixture was allowed to warm (exotherm) to 丨51 during the addition of 135696.doc -50- 200933951. The mixture was then cooled to 6 C and the ice bath was removed to warm the mixture to 23 C. The mixture was stirred at <RTI ID=0.0># </ RTI> </ RTI> </ </ > It was dissolved in dioxane, washed with water, dried over anhydrous magnesium sulfate, filtered and concentrated to afford 41········································ Synthesis of 5,5,6,6,7,7,8,8,8-tridecafluorooctyl)mucosate (&quot;PCSA-7&quot;) f2 f2 o 0 F2 F2 p2 f2 in 500 ml In a 3-necked flask, the compound was cis, cis-muconic acid (?11^) (0.784 g, 5.52 mmol) was suspended in 15 〇 111 丨 di-methane under nitrogen. The mixture was stirred under nitrogen and ice. The mixture was cooled to 2. The mixture was treated with hexanes (2. <RTI ID=0.0></RTI> </RTI> <RTIgt; </RTI> <RTIgt; </RTI> <RTIgt; It was cooled in an ice bath and treated with additional hexanes (28 gram, 22 mM). The mixture was allowed to warm to 23. (:, and it became thinner after 4 hours) The suspension was stirred at 23 ° (: 18 hours to give a clear pale orange solution. Concentrated and placed under high vacuum to give an orange solid. The solid was dissolved in 150 ml of di-methane under nitrogen. Cool in a bath and treat with 1^1, 111, 21^21^ perfluoro-1-octanol (8 1 (!1^11) (4.02 g, 11.0 mmol) followed by triethylamine (4.45) A solution of gram, 44 mmol was obtained. The mixture was stirred for 20 min and the ice bath was removed and the mixture was warmed to 135 696.doc -51 - 200933951 23 ° C » TLC was displayed at 23 ° C for one hour The main product was stirred. The mixture was stirred at <RTI ID=0.0># </ RTI> </ RTI> </ RTI> <RTIgt; And concentrated to give 378 g of a light brown solid. The solid was dissolved in ethyl acetate and was chromatographed on a silica gel column (5 cm diameter x 16 cm length) using 15% ethyl acetate in hexane. Obtained 93 g of an orange solid. Recrystallized from several milliliters of toluene to give 1.07 g. Light brown solid * H NMR (CDC13):. Δ (ppm): 7,33 (m, O 2H), 6.21 (m, 2H), 4.49 (t, 4H), 2.52 (m, 4H).

Example IS This example shows the contact angle measurement of a film formed by PCSA-6 on a non-cavity transport layer. The hole transport layer was a crosslinkable copolymer of triphenylamine, dioctyl and diphenylethene prepared as in Example 1 (&quot;HT-1&quot;). The HT-1 layer was treated with a purified PCSA-6 solution in perfluorooctane in 2% (w/v) and spun at 60 rpm for 60 seconds. The light film is visible under white light. The wafer was irradiated with 248 nm light at i 5 mW/cm 2 for 1800 seconds (a light film of 2.7 J/cm 2 was still visible. The wafer was baked at 175 ° C for 300 seconds. The film was invisible) using an amount of anisole The contact _ angle was measured before the angle of 57-61 degrees. The wafer was washed 1 times with perfluorooctane and air dried. The contact angle was measured using anisole to obtain 63-67. The previous angle was advanced. Example 16 Description of this example The contact angle of the film formed by PCSA-1 on the hole transport layer was measured. The hole transport layer was triphenylamine, dioctyl and diphenyl 135696.doc • 52· 200933951 Crosslinked Copolymer (&quot;ΗΤ-1&quot;) ΗΤThe ΗΤ-l film wafer was treated with 5% (w/v) solution of purified PCSA-1 in perfluorooctane and spin coated at 6 rpm 60 seconds. The light film is visible under white light. The wafer is irradiated with 248 nm light at 1.5 mW/cm2 for 1800 seconds (2.7 J/cm2 dose). The light film is still visible. The wafer is baked at 175 °C. 300 seconds. The film was not visible. The benzoquinone was measured - the contact angle was 57-61 degrees before the angle was taken. The wafer was washed with perfluorooctane for 1 〇 and air dried. The contact angle was measured with anisole. 63-67 Previous advancement. Example 17 © This example shows the contact angle measurement of a film formed of PCSA-6 on glass. 2% (w/v) of the blank glass wafer as purified PCSA-6 in perfluorooctyl The solution was treated and spin coated at 600 rpm for 60 seconds. The light film was visible under white light. The wafer was irradiated with 248 nm light at 1.5 mW/cm2 for 1800 seconds (2.7 J/cm2 dose). The light film was still visible. Round at 175. Bake for 3 sec. under the armpit. The film is not visible. Use the benzoquinone to measure the contact angle to get 48_53. Before the advance angle and 27_35. Then retreat. Example 18 (control) ❹ This control shows the contact of the glass Angular measurement. Use the anisole to measure the contact angle to obtain 19-22. Before the angle of advance and 11_14. Then the angle of retreat. Example 19 This example shows the contact angle measurement of the film formed by PCSA-6 on gold. It was treated with purified PCSA-6 in a 2% (w/v) solution in perfluorocarbon and sprayed at 600 rpm for 60 seconds. The pale film was visible under white light. The wafer was 248 nm light at 1.5 mW/cm2. Irradiation for 1800 seconds (2.7 J/cm2 dose). 135696.doc -53- 200933951 The light film is still visible. The wafer is baked at 175 ° C for 300 seconds. The film is not visible. The benzotribe measurement contact angle was obtained before the 69-71 degree advance angle and 37-41. (Initial adhesion) and then the exit angle. The wafer was washed 10 times with perfluorooctane and air dried. The contact angle was measured with anisole. Get 64-65. Before entering the corner and about 35. (Initial • Adhesion) Back angle. The wafer was washed 1 time with 1,1,2-tri-trifluoroethane and air dried. The contact angle was measured using anisole to give 57-59. The angle of advance before the angle of advance and 27-34° (initial adhesion). Example 20 (Control) © This control shows the contact angle measurement of PCSA-6 on gold without UV irradiation. The gold wafer was treated with purified PCSA-6 in a 2% (w/v) solution in a full gas sinter and spin coated at 600 rpm for 60 seconds. The pale enamel is visible under white light. The wafer was baked at 175 ° C for 300 seconds. The film is not visible. The contact angle was measured using anisole to give an advance angle of 17-21° and about 20. Then retreat. Example 21 (Control) This control shows the contact angle measurement of untreated gold. © Benzene ether to measure the contact angle to obtain 5-1 0. Before entering the corner. Example 22 This example shows the contact angle measurement of a film formed of PCSA-6 on a hole transport layer. The hole transport polymer is a non-crosslinkable triarylamine polymer (&quot;HT-2&quot;) 30 A 30 mm glass test piece was spin-coated with a 0.35 wt/vol% solution of HT-2 in toluene. The resulting film was dried at 20 (TC for 30 minutes. The HT-2 membrane was treated with a purified PCSA-6 in 2% (w/v) solution in perfluorooctane and at 6 rpm 135696.doc. 200933951 Spin coating for 60 seconds. Light film is visible under white light. The wafer is irradiated with 248 nm light at 1.5 mW/cm2 for 1800 seconds (2.7 J/cm2 dose). The light film is still visible. The wafer is at 175 °C. Bake for 300 seconds. The film is not visible. The contact angle of HT-2 is measured on the glass using anisole to obtain 62-70. The previous angle has strong viscosity and slipperiness. Example 23 (Control) This example shows Contact angle measurement of the film formed by HT-2. • The contact angle of the film formed of HT-2 was measured on glass using anisole to obtain a ❹ 10-13° advance angle. Example 24 This example shows a hole On the transport layer, cis-cis-bis(3,3,4,4,5,5,6,6,7,7,8,8,8-dodecafluorooctyl) muconate PCSA-7 is formed. The contact angle of the film was measured. The hole transport layer was a crosslinkable copolymer (&quot;HT-i") of triphenylamine, dioctylfluorene and diphenylethylene ruthenium prepared as in Example 1. HT-1 The membrane was treated with a purified PCSA-7 solution in perfluorooctane at 05〇/〇 (w/v) and at 12〇〇 Rotate φ φ for 60 seconds. Light film is visible on the wafer. The wafer is irradiated with 365 nm light at 45 mW/cm for 62 seconds (2.7 J/cm2 dose). The light film is still visible. Bake for 300 seconds at C. The film is not visible. The contact angle is measured using anisole; the angle of advance is 3 5 41. The wafer is washed with perfluorooctane 10 times and air dried. The contact angle was 35_42. The previous advance angle. Example 25 This example shows the contact angle measurement on a film formed on a hole transport polymer formed from a mixture of fluorinated oligomers constituting an unsaturated polybasic acid fluorocarbon. This example additionally shows The ungrafted material is removed by washing rather than by thermal evaporation. 135696.doc •55· 200933951 The use of cobalt-catalyzed chain transfer allows compounds 3,3,4,4,5,5,6,6,7,7, 8,8,8-dodecafluorooctyl methacrylate condensed polymer (Gridnev and Ittel, &quot;Catalytic Chain Transfer in Free-Radical Polymerizations/'C/zew. ...v.,/0/(72), 3611 -3659 (2001)) to obtain a polymer mixture having the following structure: F2

F2

Vcf3 f2 f2 f2 ❹

分子量v\c/C, c/C, cxf3 f2 f2 f2 The molecular weight distribution of the product is mainly terpolymer (n=2), but the range can be as high as ten-polymer. The hole transport polymer was triphenylamine, dioctylfluorene and diphenylethylene crosslinkable copolymer (&quot;HT-1&quot;) prepared as in Example 1. The polymer mixture mixture was then spin coated (600 rpm, 6 〇 see) onto the surface of the hole transport layer of three different attached test pieces in a 1 wt/vol% solution in perfluorooctane. A test piece was then exposed to ultraviolet light in a 248 nm wavelength for 15 minutes to produce an exposure dose of 2.7 J/cin2. The second test piece was exposed to ultraviolet light at a wavelength of 248 nm for 15 minutes to produce an exposure amount of 2.7 J/cm2. The third test piece is not exposed to ultraviolet light. All three test pieces were then rinsed with three 0.5 ml portions of perfluorooctane to remove any soluble material. The sample was then gradually warmed at 50 ° C for 2 min to remove perfluorooctane and then cooled to room temperature. Using the RomfHart contact angle goniometer, the forward contact angles were measured on the surface of the three specimens using anisole to obtain 43·44, 38_4〇 and 8_14, respectively. The result. The final value is the same as the untreated test piece, so the rinse is complete. Two 135696.doc -56 - 200933951 The value of the irradiated sample clearly indicates that the material is photochemically grafted to the surface. Example 26 (Prophetic) This example demonstrates the substituted 2,2-dimethyl-4-methylene glutarate-bis (3,3,4,4,5,5,6 fluoroalkyl alcohol) , 6,7,7,8,8,8-tridecafluorooctyl) 2,2-dimercapto-4-methylene sebacic acid g possible synthesis.

0 F2 f2 c, F2 Preparation of dimethyl 2,2-dimethyl-4-methyleneglutarate by catalytic chain transfer oligomerization of decyl methacrylate in the presence of a strong acid deesterification catalyst The fluoroalcohol shown heats the sterol ester. Release of two equivalents of sterol to produce bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) 2,2-dimethyl-4 - Yttrium glutarate. Example 27 (Prophetic) This example shows that on the hole transport layer, by bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl The low surface energy of the film formed by 2,2-dimethyl-4-arylene glutarate.

135696.doc -57- 200933951 The hole transport layer is a crosslinkable copolymer of triphenylamine, dioctyl and distyrylfluorene prepared as in Example 1 ("ΗΤ·1&quot;). Preparation from Example 丨1 A 3% (wt/vol) solution of the product in perfluorooctane. The solution was then spin coated (1200 rpm '60 sec) onto the surface of the hole transport layer. The test piece was then exposed.

Ultraviolet light (30 min) at 2.7 J/cm2 at 248 nm, followed by baking at 65 °C for 2 min and baking at 130 °C for 2 min. Contact with R〇m0-Hart; Angle goniometer used to measure the advancing contact angle with anisole on these surfaces to obtain an over 35° result.实例 Example 28 This example illustrates the contact angle measurement of a film formed from PCSA-6 on a photoinitiator layer. The hole transport layer is triphenylamine, dioctyl and stilbene-based crosslinkable copolymer (&quot;HT-1&quot;). The glass wafer coated with HT-1 film was treated with a solution of Irgacure 184 (Ciba) dissolved in diethyl ketone (DEK) and coated at 600 rpm for 60 seconds. The resulting film was then treated with a 2 w/v% solution of PCSA-6 dissolved in perfluorooctane and spun at 600 rpm for 60 seconds. The © wafer was irradiated with 248 nm light at 1.5 mW/cm2, and then the wafer was baked at 175 ° C for 300 seconds. The contact angle was measured using phenyl ether. The table below shows the contact angles measured using experiments with different exposure doses and Irgacure 184 concentrations (for comparison purposes, some experiments without applying Irgacure). It can be seen that the photoinitiator layer generally improves the contact angle at all exposure doses and allows for a contact angle of λ (or greater) as obtained for the contact angles obtained at higher exposure doses in the absence of the photoinitiator layer. . 135696.doc -58 - 200933951 Dose (J/cm2, 248nm) Irgacure 184j agronomic degree (w/v %) in DEK Advancing contact angle 2.700 0.0 62° 0.900 0.0 55 0.450 1.0 72 0.450 0.6 71 0.450 0.2 57 0.450 0.1 59 0.220 1.0 74 0.220 0.6 73 0.220 0.0 28 0.110 1.0 65 0.110 0.6 61 0.110 0.0 20 0.055 1.0 50 0.055 0.6 30 0.055 0.0 22 0.000 1.0 20 0.000 1.0 13 0.000 0.6 29 0.000 0.6 30 0.000 0.2 14 0.000 0.1 14 ❹ Example 29 Ο This example shows bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-hex-2-(indenyl)-ene-4- Synthesis of alkyne-1,6-diester (&quot;PCSA-9"). The procedure used was adapted from the following reference: V. V. Ramachandran et al. Tetrahedron Letters 46 (2005) 2547-2549 〇〇

-CH2CH2(CF2)5CF3 ο 111,111,211,211-perfluoro-1-octanol (10.1 §, 27.7 111111〇1) and propyne 135696.doc •59- 200933951 acid (1·70 mL, 27.7 Ment) was dissolved in di-methane (15 mL) and the resulting solution was cooled under nitrogen to (TC.sub.2) was added dicyclohexylcarbodiimide (5.72 g, 27.7 mm 〇i) over a period of hr. And a solution of p-dimethylaminopyridine (0.034 g, 0.28 mmol) in dioxane (15 mL), then the mixture was warmed to room temperature and a pale solid (dicyclohexylurea) was precipitated. The reaction mixture was stirred overnight and then filtered to remove dicyclohexylurea and the filtrate was concentrated in vacuo to afford crude product as a red oil. 150% of hexanes. The crude product was chromatographed on a Shixi gum column to provide 8.31 g of yellow & oily (3,3,4,4 5,5,6,6,7,7,8,8 8_tritrifluorooctyl) Propiolate (72°/. yield). (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)propynoic acid The ester (2 〇 6 g, 4.95 mmol) was dissolved in di-methane (5 mL) under nitrogen and cooled to EtOAc. Wherein 1,4-diazabicyclo[2,2,2]octane (0.0056 g, 0.0495 mmol) was added. The resulting dark brown solution was stirred at 〇 ° C for 2 〇 min and then condensed to afford a light brown solid The crude product was chromatographed on a 15 cm x 5 ccm silica gel column using 1 〇〇/◦ acetic acid ethyl acetate to provide 双91 g as a white solid double (3,3,4,4,5,5,6 ,6,7,7,8,8,8-tridecafluorooctyl)·hex_2_(e)·en-4-yne-1,6-diester (&quot;PCSA-9&quot;) (93 % yield). 4 NMR (CDC13) δ 6.80 (d, 1H, C//=CH,), 6.45 (d, 1H, CH=C/T), 4.52 (multiple peaks, 4H, OCH2), 2.52 ( Multiplet, 4H, OCH2Ci/2) Example 30 This example shows the contact angle measurement of a film formed by PCSA-9 on a hole transport layer after exposure to 248 or 365 nm light and baking. For the preparation of triphenylamine, dioctylfluorene and distyryl group as in Example 1, the first can be 135696.doc -60- 200933951

The copolymer (&quot;ΗΤ-Γ') prepared a solution of PCSA_9 in 2% 〇ν/ν) in all a octane. 0.0814 mL of this solution was placed in a Petri dish and the solvent was evaporated. A 3 mm glass test piece coated with ruthenium (prepared as described in the Examples) was attached to the inside of the Petri dish cover. Place the Petri dish on the Petri dish and place the glass test piece facing down. The ice/brine bath was placed on a Petri dish lid to allow it to cool. The Petri culture was placed on a hot plate at 190 ° C for 90 seconds during which pcSA9 was evaporated and vapor deposited on the inside of the Petri dish lid and on the HTq coated glass coupon. The total amount of pcSA9 deposited on the HT-1 coated glass test piece was about 〇〇2. The test piece was exposed to light at 248 or 365 nm, and then baked at 19 ° C for 5 min. The contact angles before the measurement using anisole are summarized in the following table: Dose at 248 nm (J/cm2) Advancing contact angle (°) 0.00 23 0.05 48 0.10 53 0.50 71 1.00 68 2.50 82 0.0 17 0.1 23 0.3 ~ 24 0.5 36 1.0 42 2.0 50 5.0 71 lo.o - 70 Example 31 This example illustrates the dicarboxylate derived from acetylene, bis (3,3,4,4,5,5,6,6,7,7 , 8,88_Tetrafluorooctyl) B. The synthesis of the two traitors (&quot;PCSA-10&quot;). ❹ 135696.doc -61 · 200933951 f3c

F2 F2

e

Add 1 孖, 1 孖, 2//, 2 --perfluoro-1-octanol to a 3-neck 25 〇 111 [round bottom flask equipped with a stir bar and inlet air condenser and outlet under nitrogen flow. (25.5 g '70 mmol 'DuPont), acetylene dicarboxylic acid (eight 1 (114 (:11,7 &lt;^-45-0) (3.992 g '35 mmol) and p-TSA (0.57 g, 3 mmol), The slurry was obtained. The mixture was slowly warmed to 115 t, and the solid was dissolved between 100 and ll ° C to give a pale yellow solution. Heating was continued at 115 ° C for 24 hours. The solution was cooled under a nitrogen stream and then dissolved in diethyl ether (about A yellow solution was obtained in 50 mL of the solution. The solution was washed with a saturated aqueous solution of NaHC 3 (50 mL) and immediately turned into a dark brown solution. The washing was repeated twice. The part with the product was placed on the MgS〇4. Stir vigorously for 15 min to dry, then decanted. The solution was passed through a neutral-grade oxidation column (about 3 cm) to produce a dark layer on top of the oxide and a yellow solution. The solution was stripped to dryness to give a pale yellow color. Viscous solid. Sublimation of the product gave a white solid. Example 32 This example shows a double layer on a transport layer (3,3,4,4,5,5,6,6,7,7,8,8,8 - Measurement of the contact angle of the intermediate film formed by pCSA_l acetylene dicarboxylic acid pCSA_l. Preparation of a 1% (wt/v〇1) solution of acetylene dicarboxylate in perfluorooctane. 600 RPM was spin-coated on the χ1χ coated wafer described in Example 5 for a time period of 60. The dose shown in the table below was irradiated at 248 nm. Then it was baked at wc for 5 min^(4) 5_ Measure the angle and display the results in the table below. 135696.doc -62 - 200933951 UY irradiation contact angle range, mJ/cm2 (forward contact angle) 0 23-27 32 37-40 ' 60 43-50 112.5 51 -56 ' 225 62-67 450 59-65 ~ 900 61-67 2700 66-73 The contact angle is dose dependent, increases rapidly under low exposure and approaches maximum under prolonged exposure.

EXAMPLE 33 This example illustrates a trisubstituted olefinic diortole ester, bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) 2 Synthesis of _phenyl cis-succinate (&quot;PCSA-11&quot;).

Add 1//, 1//, 2//, 2;/-all gas-1-xin to a 3-neck 250 mL round bottom flask equipped with a stir bar and an inlet dry condenser and outlet under nitrogen flow Alcohol (25.5 g, 70 mmol), phenyl maleic anhydride (Aldrich, fascination 35-7) (5.22 g, 30 mmol) and P-TSA (0.57 g, 3 mmol) gave an orange-brown slurry. The mixture was slowly warmed. All substances are at about 8 inches. The underarm was dissolved to give a reddish brown clear solution. The sample was further heated to about 110 C and a slight reflux was obtained for one hour. The heating is increased to 丨5〇. It lasts for 48 hours. The reaction solution was sampled for gc/MS analysis, which revealed that *MAn was completed 135696.doc • 63 - 200933951 Total reaction, but a small amount of alcohol remained. The solution was allowed to cool under a loss of flow and then dissolved in ethyl acetate (ca. 50 mL) to give a brown solution. The solution was washed with a saturated aqueous solution of NaHC 3 (3×50 mL). The ethyl acetate fraction with the product was placed on a MgSCU and stirred vigorously for 15 min to dry. The suspension was filtered and the solvent was removed from the filtrate under reduced pressure to give a yellow brown oil. The oil was dissolved in a minimum of diethyl ether and then cooled in dry ice overnight. The solid was dissolved in a minimum amount of diethyl ether and passed through a neutral alumina column (about 3 cm) to give a dark layer on top of the oxidized. The solution was poured to dryness to give bis(3,3,4,4,5,5,6,6,7'7,8,8,8-tridecafluorooctyl)-2-phenylmaleic acid The milky white crystalline solid of the ester. Example 34 This example illustrates the use of a trisubstituted olefin dicarboxylate vapor coated substrate. An ice/brine bath was prepared in a stainless steel bowl to give a temperature below 〇t:. The hot plate was preheated to a surface temperature of 190 °C. a solution of bis(3,3,4,4 5,5,6,6,7,7,8,8 8_dodecafluorooctyl) 2-phenylbutyric diester pcSA l丨 in 8 (0.25%, w/v) sample (300 μΙ〇 applied to the bottom of the Petri dish and allowed Vertrel® to evaporate (1-2 minutes) to facilitate spreading over a larger area of the Petri dish The solution was applied. The single deposited substrate described in Example 5 was adhered to a Petri dish lid with Kapton® tape (acrylate adhesive). The lid was placed in a petri dish containing phenyl maleate. On the bottom, the ice/salt bath was placed on the Petri dish combination for three minutes to cool the lid and substrate. The bath and Petri dish were placed in the center of the hot plate for 9 sec. After cooling to room temperature The coating material can be observed to be transferred from the Petri culture bottom 135696.doc •64· 200933951 to the lid and substrate. Then the sample shown in the table below is exposed to 248 nm radiation. Then the sample is placed under ^纟^ Bake for 5 minutes. Then contact angle measurement was performed and reported in the table below. UV irradiation mJ/cm2 average CA, ° (advancing contact angle) 0 25 450 44 900 45 2700 66 The contact angle (&quot;CA&quot;) is dose dependent, increases rapidly under low exposure and increases slowly with long exposures. 〇Example 35 The purpose of this example is to illustrate substituted olefins at 1,1 _ position Di(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)2-benzylidene malonate Synthesis of (&quot;PCSA-12&quot;). Under a nitrogen flow, equip a 3-neck 250 mL round bottom flask with a stir bar and inlet and outlet. Add to it (:1//, 1//, 2// 2//-perfluoro-1-octanol (364 g, 100 mmol), malonic acid (5.203 g, 50 mmol) and p-TSA (0.57 Ο g '3 mmol). The mixture was warmed and about A clear, colorless solution was obtained at 100 ° C. The sample was heated to 115 ° C for 24 hours. The solution was cooled under a stream of nitrogen and then dissolved in diethyl ether (about 50 mL) and sat.

Wash with NaHC 3 aqueous solution (3 x 50 mL). The time to reach each layer separately • Long. The ether solution with product was filtered through a bed of neutral alumina (about 3 cm). This step causes the solution to be significantly lighter in color and leaves a ribbon on the alumina. The ether solution was then stripped on a rotary evaporator to give an almost colorless liquid. Place the liquid on the still vacuum line and remove the remaining volatile materials from the system at room temperature and 135696.doc -65- 200933951. This yields about 29 g (73%) of the desired bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)malonic acid ester. F2 f2 f2 f2 f2 • ΛΛ f2 f2 f2, c, c, F2 F2 Stir 0.7146 g piperidine (8.358 〇^/WC, mmol) catalyst, i 4369 g benzaldehyde in a 100 mL 3-neck flask at room temperature ( 13 543 Li Wei 1) and 1〇2〇61 g Double (3'3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)malonic acid Ester (12.818 ❹ 匪〇1). Solids and liquids were observed during the entire reaction period. Two hours later, some of the liquid mixed with acetone was removed to obtain a GC sample indicating the absence of benzaldehyde. After about 24 mL of additional benzoquinone was added for 24 hours, the reaction was stopped and the solvent was removed on a rotary evaporator. The residue was dissolved in petroleum ether and cooled in dry ice overnight. The sample is then vacuum filtered to yield the desired white solid bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-2-benzylidene Malonate.

Example 36 The purpose of this example is to illustrate the spin (3'3,4'4,5,5,6'6,7,7,8,88-tritrifluorooctyl) 2 by spin coating, υν exposure and heat treatment. The contact angle of the methyl ether on the subunit malonate vinegar PCSA-12 film. By the method of Example 5, bis(3,3'4,4,5,5,6,6,7,7,8,88-tridecafluorooctyl)2·benzylidene malonate was 1% (wt/v〇i) of the solvent-coated RPM in Vertrel XF was spin-coated on the substrate for 6 〇s. The wafer was irradiated with 248 135696.doc -66-200933951 nm and at 175 °C. Bake for 5 minutes. The contact angle is then measured. Irradiation dose mJ/cm2 contact angle range. (Advancing contact angle) 0 14-20 32 18-21 60 19-25 112.5 23-30 225 25-31 450 27-32 900 25-30 2700 28-35

The contact angle increases rapidly at low doses, but at high doses, the final contact angle is moderate. Example 37 This example describes the bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-1-nonylbenzenesulfonyloxyethyl group- Synthesis of 1,2-dicarboxylate (PCSA-13). 0 OH F2 F2 F2 &gt; —(+2HO^^C, CrC, C'C, CF3 + p-TSA HO 〇 F2 F2

f2C^CF2 E,Z isomerization not specified F2l^eF Under a nitrogen flow, a C6 alcohol (12.7548 g, 35.03 mmol) was added to a 3-neck 100 mL round bottom flask equipped with a stir bar, an inlet, a dry condenser and an outlet. ), ADCA (2.0009 g, 17.54 mmol) and p-TSA (3.3289 g, 1 7.50 mmol) to initially form a pale yellow mixture. As the mixture was heated to 1 ° C, a yellow solution with an oily appearance was formed. The solution was heated at 135696.doc -67 - 200933951 U5t: for 24 hours. After 8 hours, the solution was medium brown. The solution was dark brown before the reaction was gradually completed. The solution was dissolved in 5 乙醚 diethyl ether. It was then washed with a saturated NaHC 3 solution (3 x 5 mL). As the NaHC03 solution was added to the mixture t, the color of the layer was changed. [The ether layer was then placed on the MgS 4 and stirred vigorously to dry, followed by decantation. The solution was then passed through a neutral grade alumina (about 3 cm) to produce a / wood brown layer on top of the alumina and a light brown-medium brown solution. The ether was then stripped to give an orange solid. Obtain a solid in the gas imitation] ^ River scale. The solid is then recrystallized from a mixture of ethyl (tetra)isopropanol. After the sample was allowed to cool on dry ice, the sample was vacuum filtered to give a pale yellow solid. Place this sample in a pot under a vacuum line. The filtered remaining liquid was placed on a rotary evaporator to obtain a white solid. The NMR spectra of the two solids were obtained. EXAMPLE 38 This example describes the photo-grafting of bis(^^ with di-trifluorooctyl octyl toluene oxyalkylene ethyl q,2.dicarboxylate (pcsA l3). ❿ Double C6 2_(曱The 1% (wt/vol) solution of benzenesulfonyloxy) maleate in Vertrel XF was spin-coated on the crucible at 6 〇〇 RpM for 6 〇s. The wafer was immediately irradiated and baked according to the following table. Baked (at 248, 3〇min=2 7 ; J/Cm2; '62 sec=2.7 J/cm2 at 365(10)). Use anisole to measure contact angle' and add anisole in 1卟 increments The Rame-Han goniometer is used to measure the advancing contact angle to the wafer surface. Measurements are taken at one location on each wafer and the most consistent contact angle is recorded. 135696.doc -68- 200933951

Irradiation dose, mJ/cm2 contact angle range. (Forward contact gn-0 450 67-7^ 2700 80-8 S Example 39 This example describes four (3,3,4,4,5,5,6,6,7,7,8,8,8-ten Synthesis of trifluorooctyl)ethylidene tetracarboxylate (PCSA-14).

p-TSP

F3 肆(3,3,4,4, 5, 5, 6,6,7, 7,8, 8, 8-trifluorooctyl) Ethyl-1,1,2,2-tetracarboxylic acid ester

36 g (99 111〇1〇1) out of a 3-neck round bottom flask equipped with a stir bar, nitrogen bubbler and air condenser, 211, 2 to perfluorooctyl alcohol, 5 § (15.8 mmol) The combination of tetraethyl ethyl tetracarboxylate and g-p-toluenesulfonic acid. initial,

There appears to be a foam on the reaction surface. However, as the reaction is heated to 10 ° C, the foam is reduced and it turns out to be a solid floating in the liquid. As the probabilities increase, the sample becomes clear. After about 24 hours, the progress of the reaction was monitored using nmr and NMR indicated that excess reactants remained. Hold the sample at temperature for a period of two weeks, periodically add more 111, out, 2 to 211-perfluorooctyl alcohol to supplement the 1Η'1Η'2Η taken by the nitrogen blowing and the released ethanol reaction. , 2 Η - all gas octanol. After cooling, the sample was dissolved in a 5 〇 匕 。 puzzle. The crucible is then washed with about 50 mL of sodium bicarbonate to produce a yellow liquid. The yellow liquid is converted to a clear liquid by oxidizing (about 3 em). The ether was stripped off on a rotary evaporator. #白凝胶 (tweet-like) placed in a vial and pumped under high vacuum for a period of two days. The final NMR of the material 135696.doc -69- 200933951 indicates that it is mainly the desired tetrafluoroalkyl ester (4·51 ppm) doped with fluoro(monoalkyl) monoethyl ester (the fluoroalkyl ester is 4.39 and ethyl ester). Is 4.23). The ratio of 40:12:4 of the three resonances indicates that the ratio of the two products is i〇: 4 or 28% monoethyltetraacetate. Example 40 - This example describes four (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-extended ethyltetracarboxylate (PCSA- 14) Light grafting. * Four C6 exoethyl tetracarboxylate (the material described in Example 39) was filtered in a solution of Vertrel © XF (0·0832 g solids / total 8.3105 g) and spun on the HTL at 600 RPM for 60 hours. s. The wafer is immediately illuminated and baked according to the table below. The contact angle was measured using anisole and the anisole was added to the wafer surface in 1 increments to measure the advancing contact angle using a Rame-Hart goniometer. Measurements were taken at one location on each wafer and the most consistent contact angle was recorded. Irradiation dose, mJ/cm2 contact angle range. (Advance Contact Bar, 0 28-45 60 32-41 450 47-52 2700 69-75 / The idea is not required for all of the actions described above in the general description or examples, some specific actions may not be required and may be performed In addition to the behaviors described above, or a plurality of other acts, in addition, the order in which the acts are listed is not necessarily the order of execution. In the foregoing specification, the concepts have been described with reference to the specific embodiments. It is to be understood that various modifications and changes can be made without departing from the scope of the invention as set forth in the following claims. 135696.doc 200933951, and all such descriptions and drawings are to be regarded as illustrative and not limiting. Modifications are intended to be included within the scope of the present invention. The foregoing embodiments are described to describe benefits, other advantages, and solutions to problems. However, 'these benefits, advantages, problem solving methods, and possibly any benefits' advantages or solutions are produced. Any feature that makes it more obvious should not be considered a critical, essential or essential feature of any or all of the claims.

It will be appreciated that certain features that are described herein in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, various features that are described in the context of a single embodiment for the sake of simplicity may be provided separately or in any subcombination. In addition, the recited values in the scope of the disclosure include a slight variation that is above and below the range, which can be used to achieve substantially the same results as the values within the ranges. Further, the disclosure of such ranges is intended to be a continuous range, including each value between the minimum and maximum averages, including the fractional value that can be produced when some of the components of the value are combined with the components of the different values. Moreover, when a broader and narrower range is disclosed, the present invention contemplates matching the minimum of one range to the maximum of the other, and matching the maximum of one range to the minimum of the other. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 includes a schematic diagram illustrating a contact angle. Fig. 2 includes an illustration of an organic electronic device. [Main component symbol description] 100 Electronic device 110 Anode/anode layer 135696.doc 71 200933951 120 Buffer layer 130 Hole transport layer 140 Photoactive layer 150 Electron transport layer 160 Cathode/cathode layer 135 135696.doc -72-

Claims (1)

200933951 X. Patent Application Range: 1. A method for forming a second layer of a wrapper on a first layer, the method comprising: forming the first layer having a first surface energy; • comprising a component selected from the group consisting of α, β- Treating the first layer with a photocurable surface active composition of a material of a group consisting of a fluorinated ester of an unsaturated polybasic acid, a fluorinated quinone imine of an α,β-unsaturated polybasic acid, and combinations thereof; The curable surface active composition is exposed to radiation in a pattern to produce a cured exposed area and an unexposed area; developing the photocurable surface active composition to remove the photocurable surface active composition from the unexposed area, Producing a first layer having an untreated portion and having a treated portion in the exposed region, wherein the treated portion has a second surface energy lower than the first surface energy; and the first layer The second layer is formed on the untreated portion. 2. The method of claim 1, wherein treating the first layer comprises depositing the photocurable surface active composition on the first layer. 4. The method of claim 1, wherein treating the first layer comprises applying the photocurable surface active composition to the first layer in the form of a separate layer. The method of claim 1 wherein the photocurable surface active composition in the unexposed area is removed by treatment with a liquid. 5. As in the method of the monthly proposal 1, the blue light in the basin is known from the present, and the photocurable surface active composition in the τ忑he exposure zone is removed by evaporation. 6. The method of claim 1, wherein the polybasic acid is a polycarboxylic acid. 7. The method of claim 6, wherein the polybasic acid is selected from the group consisting of fumaric acid, maleic acid, itaconic acid, 2,2 dimethylene Polymeric acid of methyl pentanoic acid, muconic acid, 2-methylene glutaric acid, ac〇tinic acid 'acetylene dicarboxylic acid, hexa-2-ene-4-alkynic acid, methacrylic acid and combination. 8. The method of claim 1, wherein the ester is formed using an alcohol having the formula Rf〇H, wherein the carbon atom chain of the Rf group has 4 to 15 carbon atoms, and the 〇5 is contained in the side of the carbon atom. An oxo oxygen atom and at least four fluorine atoms bonded to a carbon atom of the carbon atom chain are limited to having no fluorine atom on a carbon atom having 〇H. 9. The method of claim 1, wherein the quinone imine is formed using an amine having the formula wherein the carbon atom chain of the Rf group has 4-15 carbon atoms, and 〇5 is pendant to the carbon atom. The oxygen atom and at least four fluorine atoms attached to the carbon atom of the carbon atom chain are restricted to have no fluorine atom on the carbon atom having NH2. 10. The method of claim 1, wherein the first layer is an organic polymer. 11. The method of claim 1, wherein the first layer is selected from the group consisting of metal metal oxides, glass, and ceramics. 12. The method of claim 1 wherein the organic polymer is a hole transport layer material. 13. The method of claim 1, wherein the photocurable surface active composition is selected from the group consisting of: bis(3,3,4,4,5,5,6,6,7'7, 8,8,8-tridecafluorooctyl) fumarate; bis(3,3,4,4,5,5,6,6,7,7,8,8,8-trifluoro Octyl) maleate; 1356%.doc 200933951 bis (3,3,4,4,6,6,7,7,8,8,8-undefluoro-5-oxa-octyl ) __ ester; double (3,3,5,5,6,6,7,7,8,8,8-undefluorooctyl) cis-butane diacid. Ν-4,4, 5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-+ 4- ^ , 卞-based cis-indenimide; double (3,3 , 4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) itaconic acid self-blind. Double (3,3,4,4,5,5,6 , 6, 7, 7, 8, 8, 8 - 13 gas octyl- cis cis - mukate; Double (3,3,4,4,5,5,6,6,7,7,8,8,8-trifluorooctyl))_4_(£)_稀_4 Fast-1,6 - Diacid vinegar, bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)acetylene dicarboxylic acid _; double (3,3, 4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-2-phenyl cis-butyl Acid ester; bis(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-2-ylidenemalonate; CH2CH2OCH2CH2OCF2C(H)FOC3F7) maleate; bis(CH2CH2OCF2C(H)FOC3F7) maleate; bis(CH2CH2CH2OCF2C(H)FOC3F7) maleate; double (3,3,4 , 4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)-1-toluenesulfonyloxyethyl-1,2-dicarboxylate; 3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)eethyltetracarboxylic acid 135696.doc 200933951 ester; and combinations thereof. 14. A method for fabricating an organic electronic device comprising a first organic layer and a second organic layer on an electrode, the method comprising: forming the first organic layer having a first surface energy on the electrode; Photocurable surface treatment composition comprising a material selected from the group consisting of fluorinated esters of α,β-unsaturated polybasic acids, fluorinated quinones of α,β-unsaturated-polyacids, and combinations thereof The first organic layer; *, the photocurable surface active composition is exposed to radiation in a pattern to produce an exposed area and an unexposed area; developing the photocurable surface active composition to develop the photocurable surface The active composition is removed from the unexposed zone, resulting from the unexposed zone having an untreated portion and having a treated portion of the first organic active layer in the exposed zone, wherein the treated portion has a lower than the first surface a second surface energy; and forming the second organic layer on the untreated portion of the first organic active layer. 〇15. An organic electronic device comprising a first organic active layer and a second organic active layer on an electrode, and additionally comprising a patterned photocured. Surface active composition, wherein the second organic active layer It is only present in the region which does not have the photocurable surface active composition, and wherein the photocurable surface active composition is made of a material selected from the group consisting of: α,β-unsaturated polybasic acid A fluorinated ester, an alpha, a polyunsaturated polybasic acid, and a combination thereof. 16. The method of claim 1, wherein the first layer comprises a photoinitiator. 135696.doc 200933951 1 7. The method of claim 1, wherein the first layer consists essentially of a photoinitiator. 18. The method of claim 1 wherein the photocurable surface active composition further comprises a photoinitiator. 1 9. The method of claim 1 $, , #表, where the treatment comprises solution coating. ‘ 2〇·, as in the case of claim 1, 〇1 method' wherein the treatment comprises steam coating. • 21. If the request is 1$^, the soil is in the range of visible light radiation and purple, external light radiation. ❹ 22. If requested, the method of gentleman, wood, where the radiation has a wavelength in the range of 300 to 450 nm. 23. The method of claim 1, wherein the first organic layer is a hole transport layer and the organic layer is a photoactive layer. 24. The method of claim 2 wherein the first organic layer comprises a photoinitiator and the s&quot; second organic layer is a photoactive layer. 135696.doc